CN1499286A

CN1499286A - Silver-halide colour photograph photoelement

Info

Publication number: CN1499286A
Application number: CNA2003101043858A
Authority: CN
Inventors: ��徸; 稻见义靖; 三木正章; ��һ; 细川淳一郎
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2002-10-25
Filing date: 2003-10-27
Publication date: 2004-05-26
Also published as: US6951711B2; JP2004287390A; US20040086812A1

Abstract

A silver halide color photographic lightsensitive material containing at least one compound capable of increasing photographic speed, the compound having at least three heteroatoms in its molecule, and wherein at least one layer of the silver halide emulsion layers comprises an emulsion, the emulsion consisting of a lightsensitive are occupied by tabular grains having (111) faces as main planes, the tabular grains (i) composed of silver iodobromide or silver chloroiodobromide, (ii) having an equivalent circle diameter of 1.0 mum or more and a thickness of 0.15 mum or less, and (iii) composed of core portions of 0.1 mum or less thickness free of growth ring structure and composed of silver iodobromide, shell portions having ten or more dislocation lines and phototonus silver halide emulsion wherein 50% or more in number of all the silver halide grains.

Description

Silver halide colour photographic sensitive material

Technical field

The present invention relates to silver halide colour photographic sensitive material, more particularly relate to a kind of sensitivity height and graininess is good, sharpness is high silver halide colour photographic sensitive material.

Background technology

With regard to silver halide colour photographic sensitive material,, more and more higher to the requirement of its sensitivity in order to improve colour negative film user's interests.Particularly in recent years, can often adopt specific photograph sensitivity (ISO sensitivity) at the high sensitivity film more than 800 at the minicam of convenient band lens film of also photographing simply of various conditions of exposure and band zoom function along with using gradually.

High sensitivityization by this film, the high-speed shutter photographies, astrophotography etc. that can be implemented in use telephoto lenss such as the dark indoor photography of carrying out without flashlamp, sports photography need the photography of time exposure etc., the photography of photosensitive material is broadened, and its result brings big advantages to the user.Therefore, the high sensitivityization of film is one of target as the pursuit forever of this area problem.

The high sensitivity film in past owing to be too to pursue high sensitivity, can only obtain tolerating considerably beyond the user the sort of low image quality image of boundary, so the user can only select one of them among sensitivity and image quality, the result has to select image quality and sacrifices sensitivity.

For making the photosensitive material high sensitivityization, the means that usually adopt in this area are the sizes that increase as the silver halide particle of photo-sensitive cell, more also with other high sensitivity technology.

In a single day the size of silver halide particle increases, though sensitivity has rising to a certain degree, as long as silver halide content is certain, the number of particles of silver halide must reduce, and that is to say the minimizing of counting that begins to develop, thereby existence makes the impaired greatly shortcoming of graininess.

In addition, increase the design of this silver halide particle number of per unit area, promptly, if the silver halide amount that is coated on the photosensitive material is increased, will be during this before use from the photosensitive material manufacturing after in the problem of photography property deteriorations such as the increase of initiation photographic fog, sensitivity reduction, graininess deterioration.

On the other hand, disclose recently a kind of by silver halide photographic sensitive material is contained have at least three not with the develop heteroatomic compound of main reagent reacting of oxidation, under the condition that graininess is worsened, improve the technology (for example referring to patent documentation 1) of sensitivity thus.

For making the photosensitive material high sensitivityization, the tabular silver halide particle obtains adopting gradually.About the tabular silver halide particle, its manufacture method and operation technique are open, and known its advantage is (for example referring to the patent documentations 2) such as improvement to concerning between sensitivity/graininess that comprises the rising of the look sensitizing efficient that is caused by the spectral sensitization pigment.

The performance that has the tabular particle of these advantages for raising has the people to carry out various researchs.Diameter of equivalent circle is big, the tabular particle of thin thickness be owing to can adsorb the spectral sensitization pigment in a large number, so help improving sensitivity.Though the tabular particle is thin more more can adsorpting pigment, in fact is difficult to along with the attenuation acquisition of particle thickness and the corresponding high sensitivity effect of increase of sensitizing coloring matter adsorbance.As one of its reason, can enumerate the influence of the unfavorable electron trap in the particle, disclose at present by removing this electron trap and improve the technology (for example referring to patent documentation 3) of sensitivity.

Yet, even adopt such technology,, the attenuate of tabular particle thickness is difficult to import the problems such as dislocation line that help high sensitivityization along with also can producing, can not obtain required high sensitivityization.Therefore, self-evident people are still expecting the high sensitivity technology.

On the other hand, about the sharpness of photosensitive material, known attenuate protective layer thickness just can improve.And, make the reduced thickness of photosensitive material by adopting the tabular particle according to record, (for example referring to patent documentation 4) can promote clearness.If but the reduced thickness of tabular particle, the light scattering that self is caused by the tabular particle will increase.Therefore when reducing the thickness of employed tabular particle, the problem of the sharpness decline of photosensitive material can appear on the contrary.

By above-mentioned situation as can be known, bring into play the advantage of tabular particle and the photosensitive material that obtains high sensitivity and high definition is unusual difficulty.

Patent documentation 1: the spy opens the 2000-194085 communique

Patent documentation 2: No. 4434266 instructions of United States Patent (USP)

Patent documentation 3: the spy opens the 2001-281778 communique

Patent documentation 4: the spy opens flat 5-034857 communique

Summary of the invention

The problem that exists in the above-mentioned prior art develops in order to solve just in the present invention, and purpose is to provide a kind of sensitivity height and graininess is good and sharpness is high silver halide colour photographic sensitive material.

The present invention seeks to reach by following method.

(1) a kind of silver halide colour photographic sensitive material; on support, have respectively in the silver halide photographic sensitive material of one deck sense indigo plant silver halide emulsion layer at least, the green property silver halide emulsion layer of sense, the red property silver halide emulsion layer of sense and protective seam; it is characterized in that; at least contain in this silver-halide color photoelement and have three heteroatomic compounds that are used to increase the photograph sensitivity in a kind of molecule at least; and contained emulsion is in the one deck at least in this silver halide emulsion layer, by

(i) form by iodine silver bromide or chlorine iodine silver bromide,

(ii) and diameter of equivalent circle more than the 1.0 μ m, thickness below 0.15 μ m,

(iii) and by not having year wheel construction and thickness is being made up of the iodine silver bromide below the 0.1 μ m

Core and have the shell portion of ten above dislocation lines to constitute, and be the dull and stereotyped particle of first type surface with (111) face, the photonasty silver emulsion more than 50% of all silver halide particle numbers occupied.

(2) silver halide colour photographic sensitive material of record in (1), the thickness summation that it is characterized in that described protective seam is below 3 μ m.

(3) silver halide colour photographic sensitive material of record in (1) or (2), it is characterized in that having at least in the molecule three heteroatomic compounds that are used to increase the photograph sensitivity is 1,3,4, the 6-purine (tetraazaindene) based compound.

(4) silver halide colour photographic sensitive material of any one record is characterized in that in (1)～(3), has three heteroatomic compounds that are used to increase the photograph sensitivity in the molecule at least, is by remembering general formula (A) or the compound of (B) representing down.

[changing 1]

General formula (A)

In the general formula (A), R ₁Expression hydrogen atom or substituting group.Z represents to form the required non-metallic atom group of five Yuans azoles that contains 2～4 nitrogen-atoms, and this azole also can have substituting group (comprising condensed ring).X represents hydrogen atom or substituting group.

[changing 2]

General formula (B)

In the general formula (B), Za represents-NH-or-CH (R ₃The respectively independent expression-C (R of)-, Zb and Zc ₄)=or-N=.R ₁, R ₂And R ₃The special substituent constant σ of independent respectively expression Hamann value is in the electron withdraw group more than 0.2, below 1.0.R ₄Expression hydrogen atom or substituting group.Wherein, in formula, there are two R ₄Occasion under, two R ₄Can be identical or different.X represents hydrogen atom or substituting group.

Embodiment

Below just the present invention be described in more detail.

At first illustrate and have three heteroatomic compounds that the photography sensitivity increases (following also be called compound of the present invention) that make in the molecule of the present invention at least.Though wherein said heteroatoms also comprises any atom beyond de-carbon and the hydrogen, preferred nitrogen, sulphur, phosphorus and oxygen.

When compound of the present invention is heterocycle, said heteroatoms exists more than three in the component part of ring system, perhaps at least one heteroatoms is present in the component part of ring system, and has two above heteroatomss on the position that the ring system outside is promptly separated by a non-conjugated singly-bound and ring system at least or in other substituent part of ring system.

The sensitivity increase of photosensitive material is meant that S0.2 increases more than 0.02 among the present invention, preferably increases more than 0.03, more preferably increases more than 0.04.So-called S0.2 represents, the photosensitive material that the developing method put down in writing according to embodiment 1 is developed forms the logarithm value of inverse of the exposure of photographic fog+0.2 concentration.The so-called compound that increases sensitivity is meant, the S0.2 numerical value when photosensitive material contains this compound is compared when not containing this compound, can improve the compound more than 0.02.

Light-sensitive silver halide layer or the non-photographic layer of compound of the present invention in photographic layer is all applicable, but is preferred in the light-sensitive silver halide layer.

The compounds of this invention is used for the light-sensitive silver halide layer and photographic layer is divided under a plurality of layers the situation of different sensitivity,, is preferred in the highest layer of sensitivity though can be used for the layer of any sensitivity.

In non-photographic layer, use under the occasion of The compounds of this invention, preferably be used in be in the red property layer of sense and feel between the green property layer or feel green property layer and sense indigo plant layer between the middle layer on.

About in photosensitive material, adding the method and the not specially provided for of The compounds of this invention, the method, the solid dispersion method that disperse with common emulsification such as high boiling organic solvent wherein arranged, be dissolved in the organic solvent such as methyl alcohol and add the method in the coating fluid, the method for adding when prepare silver emulsion etc. to, but preferably utilize the emulsification dispersion to import to method in the photosensitive material.

Also comprise in the compound of the present invention and can emit the compound of the rarest three heteroatomic compound residues, and preferably use it with developing main reagent oxidation precursor reactant.

There is no particular restriction about the content of The compounds of this invention, but preferably contain 0.1～1000mg/m in the photosensitive material ², more preferably 1～500mg/m ², preferred especially 5～100mg/m ²

Under the situation that is used for the photonasty silver halide emulsion layer,, be preferably 1 * 10 with the content of one deck with respect to 1 moles of silver ^-4～1 * 10 ^-1Mole, more preferably 1 * 10 ^-3～5 * 10 ^-2Mole.

Below enumerate compound of the present invention, but be not limited to these.

[changing 3]

[changing 4]

[changing 5]

[changing 6]

[changing 7]

[changing 8]

The following describes as among the present invention more preferably compound, by the compound of general formula (A) or general formula (B) expression.

[changing 9]

[changing 10]

In the general formula (A), R ₁Expression hydrogen atom or substituting group.Z represents to form the necessary non-metallic atom group of five Yuans azoles that contains 2～4 nitrogen-atoms, and this azole also can have substituting group (comprising condensed ring).X represents hydrogen atom or substituting group.

In the general formula (B), Za represents-NH-or-CH (R ₃The respectively independent expression-C (R of)-, Zb and Zc ₄)=or-N=.R ₁, R ₂And R ₃The special substituent constant σ of independent respectively expression Hamann p value is in the electron withdraw group more than 0.2, below 1.0.R ₄Expression hydrogen atom or substituting group.Wherein, in formula, there are two R ₄The time, two R ₄Can be identical or different.X represents hydrogen atom or substituting group.

Below describe this compound in detail.With preferred skeleton in the skeleton of general formula (A) expression is 1H-pyrazolo (pyrazolo) [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole, respectively by general formula (A-1) and (A-2) expression.

[changing 11]

R in the formula ₁₁, R ₁₂The expression substituting group, X represents hydrogen atom or substituting group.

Below describe in detail general formula (A-1) and (A-2) in substituent R ₁₁, R ₁₂And X.

R ₁₁For example can enumerate halogen atom (for example chlorine atom, bromine atoms, fluorine atom), alkyl (carbon number 1～60.For example methyl, ethyl, propyl group, isobutyl, the tert-butyl group, uncle's octyl group, 1-ethylhexyl, nonyl, undecyl, pentadecyl, n-hexadecyl, 3-decyl amide propyl group), alkenyl (carbon number 2～60.For example vinyl, allyl, oleyl), naphthenic base (carbon number 5～60.For example cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 1-indanyl, cyclo-dodecyl), aryl (carbon number 6～60.For example phenyl, p-methylphenyl, naphthyl), amide group (carbon number 2～60.For example acetamido, positive amide-based small, decoyl amido, 2-palmityl amido, 2-(2 ', 4 '-two tertiary pentyl phenoxy groups) amide-based small, benzamido, nicotinoyl amido), sulfonamido (carbon number 1～60.For example methylsulfonyl amido, hot sulfoamido, benzene sulfonamido), (amino 2～60 of urea groups.For example decyl amine base carbonyl amido, two n-octyl amine base carbonyl amidos), urethane groups (carbon number 2～60.For example dodecyloxy carbonyl amido, carbobenzoxy amido, 2-ethyl hexyl oxy carbonyl amido), alkoxy (carbon number 1～60.For example methoxyl, ethoxy, butoxy, n-octyloxy, hexadecane oxygen base, methoxyethoxy), aryloxy group (carbon number 6～60.Phenoxy group, 2 for example, 4-two tertiary pentyl phenoxy groups, uncle's 4-Octylphenoxy, naphthoxy), alkylthio group (carbon number 1～60.For example methyl mercapto, ethylmercapto group, butylthio, hexadecane sulfenyl), arylthio (carbon number 6～60.For example thiophenyl, 4-dodecyloxy thiophenyl), acyl group (carbon number 1～60.For example acetyl group, benzoyl, bytyry, dodecanoyl), sulfonyl (carbon number 1～60.For example mesyl, fourth sulfonyl, tosyl), cyano group, carbamyl (carbon number 1～60.N for example, N-dicyclohexyl carbamyl), sulfamoyl (carbon number 0～60.N for example, N-dimethylamino sulfonyl), hydroxyl, sulfo group, carboxyl, nitro, alkylamino radical (carbon number 1～60.For example methylamino, diethylin, octylame base, octadecane amido), aryl amine (carbon number 6～60.For example anilino-, naphthylamine base, N-methyl-N-anilino-), heterocyclic radical (carbon number 0～60.Preferably the atom of selecting from nitrogen, oxygen, sulphur atom is as the heteroatoms that constitutes ring, and more preferably heteroatoms is in addition also with the heterocyclic group of carbon atom as ring atom, and ring person's number is 3～8, and preferred 5～6.The group of enumerating in for example following X item) and acyloxy (carbon number 1～60.For example formyloxy, acetoxyl group, nutmeg acyl-oxygen base, benzoyloxy) etc.

In the above-mentioned group; alkyl, naphthenic base, aryl, amide group, urea groups, urethane groups, alkoxy, aryloxy group, alkylthio group, arylthio, acyl group, sulfonyl, cyano group, carbamyl, sulfamoyl comprise having and also comprise the structure with the ring that contracts under substituent structure and the possible situation; as this substituting group, for example can enumerate alkyl, naphthenic base, aryl, amide group, urea groups, urethane groups, alkoxy, aryloxy group, alkylthio group, arylthio, acyl group, sulfonyl, cyano group, carbamyl and sulfamoyl.And can enumerate benzene etc. as condensed ring.

In these substituting groups, preferred R ₁₁Can enumerate for example alkyl, aryl, alkoxy, aryloxy group, more preferably alkyl, alkoxy, aryloxy group, especially preferably branched alkyl.

X represents hydrogen atom or substituting group, and substituting group can be enumerated before as R ₁₁Cited substituting group.As the substituting group of representing by X; preferred alkyl; alkoxy carbonyl group; carbamyl or with the reaction of the main reagent that develops in the group that breaks away from away; for example can enumerate halogen atom (fluorine as this group; chlorine; bromine); alkoxy (ethoxy; the methoxycarbonyl group methoxyl; the carboxyl propoxyl group; the mesyl ethoxy; perfluor propoxyl group etc.); aryloxy group (4-carboxyl phenoxy group; 4-(4-hydroxy phenyl sulfonyl) phenoxy group; 4-mesyl-3-carboxyl phenoxy group; 2-mesyl-4-acetyl group sulfamoyl phenoxy group etc.); acyloxy (acetoxyl group; benzoyloxy etc.); sulfonyloxy (mesyloxy; phenylsulfonyloxy etc.); amide group (seven fluorine amide-based smalls etc.); sulfamoyl (methane sulfamoyl etc.); alkyl oxy carbonyl oxygen (ethoxy carbonyl oxygen base etc.); carbamoyloxy (diethylamino formyloxy; 1-piperidyl carbonyl oxygen base; morpholino carbonyl oxygen base etc.); alkylthio group (2-carboxyl ethylmercapto group etc.); arylthio (2-octyloxy-uncle's 5-octyl group thiophenyl; 2-(2; 4-two tertiary pentyl phenoxy groups) amide-based small thiophenyl etc.); heterocycle thio group (1-phenyltetrazole base sulfo-; 2-benzimidazolyl sulfo-etc.); heterocycle oxo group (2-pyridine oxygen base; 5-nitro-2-pyridine oxygen base etc.); five Yuans or six Yuans nitrogen heterocyclic ring group (1-triazolyls; the 1-imidazole radicals; the 1-pyrazolyl; 5-chloro-1-tetrazole radical; 1-benzotriazole base; 2-phenyl amino formoxyl-1-imidazole radicals; 5; 5-dimethyl hydantoin-3-base; 1-benzyl hydantoins-3-base; 5; 5-Er Jia Ji oxazolidine-2,4-diketone-3-base; purine etc.); azo group (4-methoxyphenyl azo group; 4-pivaloyl aminocarbonyl phenyl azo group etc.) etc.

Preferred alkyl in the substituting group of representing by X, alkoxy carbonyl group, carbamyl, halogen atom, alkoxy, aryloxy group, alkylthio group, arylthio, with coupling active five Yuans or six Yuans nitrogen heterocyclic ring groups with the nitrogen-atoms combination, special preferred alkyl, carbamyl, halogen atom, the aryloxy group of replacement, arylthio, alkylthio group or the 1-pyrazolyl of replacement.

R ₁₂Can enumerate with regard to R ₁₁The substituting group of enumerating, preferred substituted are alkyl, aryl, heterocyclic radical, alkoxy, aryloxy group etc.More preferably substituted alkyl and substituted aryl.Most preferred substituting group is a substituted aryl.Preferably by the compound of general formula (A-3), (A-4) expression.In general formula (A-3), (A-4) ,-NHSO ₂R ₁₃Though the position of substitution be not particularly limited, preferred between position and contraposition, more preferably contraposition.

[changing 12]

In the general formula, R ₁₁With X and general formula (A-1), (A-2) synonym, R ₁₃The expression substituting group.By R ₁₃The substituting group of expression can be enumerated the front as R ₁₁The substituting group of enumerating.Preferred substituted can be enumerated substituted aryl, replacement or unsubstituted alkyl.As the substituting group of this moment, can enumerate the front as R ₁₁The substituting group of enumerating.

The preferred compound that uses in the present invention by general formula (A-1), (A-2) expression also can pass through R ₁₁And R ₁₂Form the above polymer of dimer, but also can be combined on the macromolecular chain.Preferred compound among the present invention with general formula (A-1) expression, the compound of more preferably using general formula (A-3) to represent.

General formula (B) below is described.

Compound by general formula (B) expression of the present invention can be specifically with note general formula (B3)～(B10) expression down.

[changing 13]

In the formula, R ₁～R ₄With X difference synonym in general formula (B).

Among the present invention, preferably use the compound of general formula (B3), (B4), (B5), (B8) expression, especially preferably use the compound of (B4) expression.

In general formula (B), R ₁, R ₂And R ₃The substituting group of expression is that the special substituent constant σ of Hamann p value is in the electron withdraw group more than 0.20, below 1.0.Preferred σ p value is in the electron withdraw group more than 0.20, below 0.8.The special rule of Hamann be for the quantitative discussion substituting group to the reaction of benzene derivative or be equilibrated at the empirical rule that nineteen thirty-five is proposed by L.P.Hammet.This regular reliability has obtained extensive approval now.The substituent constant of obtaining with the special rule of Hamann has σ p value and σ m value, these numerical value have been described in most general monographs, details can be referring to " Lange ' sHandbook of Chemistry " the 12nd edition of the work of J.A.Dean for example, No. 122,1079 (McGraw-Hill) and " chemical field-supplementary issue-", 96～103 pages, 1979 (Nan Jiangtang) and " Chemical Review " 91 volumes, 165～195 pages, 1991.

Among the present invention, R ₁, R ₂And R ₃Though can determine by the special substituent constant value of Hamann, but this does not also mean that the substituting group that the document that only limits to the record of these monographs has the document known numeric value, even its numerical value is unknown, but be based on the special rule of Hamann after measured occasion under, as long as belong to its scope, in being also contained in certainly.

σ p value is in the instantiation of the electron withdraw group more than 0.2, below 1.0, can enumerate acyl group, alkoxy carbonyl group, aryloxy carbonyl, carbamyl, cyano group, nitro, dialkyl phosphine acyl group, diaryl phosphono, diaryl phosphoryl, alkyl sulphinyl, aryl sulfonyl kia, alkyl sulphonyl, aryl sulfonyl etc.Also possible substituted group also can have R described later in these substituting groups ₄In the substituting group enumerated.

R ₁, R ₂And R ₃Preferred acyl group, alkoxy carbonyl group, cycloalkoxycarbonyl, aryloxy carbonyl, carbamyl, cyano group, sulfonyl, more preferably cyano group, acyl group, alkoxy carbonyl group, cycloalkoxycarbonyl, aryloxy carbonyl and carbamyl.

As R ₁With R ₂Combination, preferably work as R ₁Be cyano group, and R ₂Combination for cycloalkoxycarbonyl, alkoxy carbonyl group.

R ₄Expression hydrogen atom or substituting group can be enumerated top with regard to R as substituting group ₁The substituting group of enumerating.

Use R ₄The substituent preference of expression can be enumerated alkyl, aryl, heterocyclic group, alkoxy, aryloxy group, amide group etc., more preferably alkyl, substituted aryl, most preferably substituted aryl.Substituting group in this case can be enumerated above-named substituting group.

X is identical with general formula (A).

Below enumerate the concrete example of the The compounds of this invention of preferred use, but the present invention is not limited to these.

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

[changing 21]

[changing 22]

[changing 23]

[changing 24]

[changing 25]

[changing 26]

[changing 27]

[changing 28]

[changing 29]

[changing 30]

[changing 31]

[changing 32]

[changing 33]

By the general formula of the present invention (A) and (B) compound of expression, for example can adopt and specially to open clear 61-65245 number, spy and open clear 61-65246 number, spy and open clear 61-147254 number, spy the synthetic method of being put down in writing in the communique such as to open flat 8-122984 number easily synthetic.

Colour photographic sensitive material of the present invention has one deck sense indigo plant silver halide emulsion layer, the green property silver halide emulsion layer of sense, the red property silver halide emulsion layer of sense and protective seam at least respectively on support.Constituent parts sense chromatograph preferably is made up of the different most layers of sensitivity.

Except that photosensitive emulsion layer and protective seam, the preferred for example various non-photosensitive layers such as anti-colour mixture layer, Yellow filter layer (double as is prevented the colour mixture layer) and anti-halo layer that are provided with.

About putting in order of layer; there is no particular restriction, begins towards support successively according to protective seam, a plurality of sense indigo plant emulsion layer, Yellow filter layer (double as prevent the colour mixture layer), the green property of a plurality of sense emulsion layer, anti-colour mixture layer, the red property of a plurality of sense emulsion layer, prevents the tactic colour photographic sensitive material of colour mixture layer, anti-halo layer but can enumerate from support one lateral extent highest distance position as typical case.

Under the occasion that unit sense chromatograph is made of the different emulsion layer of sensitivity, be not particularly limited for putting in order of these layers, but generally begin to dispose sensitive emulsion layer than the distally from support.

Unit sense indigo plant silver halide emulsion layer among the present invention, under the occasion of the representative unit that different a plurality of sense indigo plant layers constitute by sensitivity, these a plurality of sense indigo plant layers also can setting not adjacent each other.

In addition, about unit sense green property silver halide emulsion layer and the red property of unit sense silver halide emulsion layer, except that the colour sensitivity of emulsion was respectively sense indigo plant and the green property of sense, other was identical with above-mentioned unit sense indigo plant silver halide emulsion layer.

For realizing high sensitivityization, except that above-mentioned Typical Disposition, also can be, feel in green property, the red property emulsion layer of sense respectively with the highest layer being arranged on of sensitivity apart from support position farthest in the different sense indigo plant of colour sensitivity.That is to say; for example from distance support position farthest, set gradually protective seam, high sensitivity sense indigo plant emulsion layer, anti-colour mixture layer, the green property of high sensitivity sense emulsion layer, anti-colour mixture layer, the red property of high sensitivity sense emulsion layer, anti-colour mixture layer, a plurality of sense indigo plant emulsion layer, Yellow filter layer (double as prevent the colour mixture layer), the green property of a plurality of sense emulsion layer, anti-colour mixture layer, the red property of a plurality of sense emulsion layer, prevent colour mixture layer, anti-halo layer.

In addition, for high sensitivityization, also can be with the high sensitivity elementary layer that constitutes by " high sensitivity sense indigo plant emulsion layer; (anti-colour mixture layer is arranged in case of necessity); the green property of high sensitivity sense emulsion layer; (anti-colour mixture layer is arranged in case of necessity); the red property of high sensitivity sense emulsion layer; (anti-colour mixture layer is arranged in case of necessity) " as the emulsion layer configuration farthest of distance support, and then set gradually the sense indigo plant emulsion layer that constitutes by one or more layers towards support, anti-colour mixture layer, the green property of the sense of one or more layers formation emulsion layer, anti-colour mixture layer, the red property of the sense of one or more layers formation emulsion layer, anti-colour mixture layer and anti-halo layer.

And then, under the high sensitivity purpose,, reflection layer can be set suitably in order to effectively utilize the light that incides photosensitive material.As reflecting material contained in the reflection layer, can enumerate with minute sized small silver halide particle and TiO ₂Inorganic crystal for representative.Under these occasions, for example use under the occasion of small silver halide particle,, preferably select the thickness of particle according to the wavelength of required light in order optionally to reflect the wavelength of incident ray.

The total amount of institute's argentiferous in the colour photographic sensitive material of the present invention, in coating weight be preferably 3.0～8.5 the gram/square metre.

There is no particular restriction about the specific photograph sensitivity of colour photographic sensitive material of the present invention, but preferably more than 640, preferred especially more than 1000 more preferably more than 800, so more helps obtaining effect of the present invention.

Below elaborate with regard to silver halide particle.

The halogen of dull and stereotyped particle of the present invention consists of the silver halide that contains silver iodide, is bromo-iodide or silver chloroiodobromide.

In the present invention, dull and stereotyped particle be meant have two relatively to the silver halide particle of parallel (111) first type surface.Dull and stereotyped particle of the present invention has the above parallel double crystal face of a twin plane or two sides.So-called twin plane is meant (111) face that is somebody's turn to do the when ion on all lattice points of (111) face both sides all has mirror.Dull and stereotyped particle of the present invention, triangular in shape when observing particle perpendicular to the direction of first type surface, sexangle or the crop that belongs in the middle of it are triangular shaped, have outside surface parallel to each other.

Be not included in the silver halide particle in the dull and stereotyped particle, comprise normal crystal grain or have the particle of the above twin plane in uneven two sides.Particle with the above twin plane in unequal two sides comprises triangle taper or bar-shaped particle.These are referred to as the non-tablet particle.

When asking the diameter of equivalent circle of dull and stereotyped particle and particle thickness, by means of replica plating with transmission electron microscope picked-up photo after, obtain diameter of a circle (diameter of equivalent circle) and particle thickness with the area that equates with the projected area of each particle parallel external surfaces.Under this occasion, particle thickness is calculated by shadow (shade) length of replica plate (replica).And with regard to the non-tablet particle, the diameter of a circle that will have the area that equates with projected area under the maximum occasion of particle projected area is as diameter of equivalent circle.The particle thickness of non-tablet particle does not for example exist as triangular pyramidal under the occasion of the face parallel with the bottom surface, with the distance on bottom surface to summit as thickness.

The non-tablet particle is little owing to specific surface area, so in case its ratio higher position is difficult to accomplish high sensitivityization, thereby not preferred.In a single day the diameter of equivalent circle of dull and stereotyped particle reduces, owing to particle size reduces to be difficult to realize high sensitivityization.In addition, in case owing to thickening specific surface area, particle will reduce, so be difficult to guarantee high sensitivity/granular ratio.

In the silver halide photographic emulsions of the present invention, all silver halide particle numbers can be more than the 1.0 μ m and particle thickness is occupied by the dull and stereotyped particle below the 0.15 μ m by diameter of equivalent circle more than 50%.In the silver halide photographic emulsions of the present invention, the preferred 50% or more of all silver halide particle numbers is more than the 1.5 μ m and particle thickness is that dull and stereotyped particle below the 0.15 μ m occupies by diameter of equivalent circle, is more than the 2.0 μ m by diameter of equivalent circle more preferably and particle thickness is that dull and stereotyped particle below the 0.15 μ m occupies.And preferably diameter of equivalent circle is below the 10 μ m, and particle thickness is more than the 0.02 μ m.

Silver emulsion of the present invention, by having above-mentioned the composition and preferable shape and be the dull and stereotyped particle of first type surface with (111) face, be the dull and stereotyped particle of silver halide that constitutes of the shell portion that there is 10 above dislocation lines at core of being made up of the iodine silver bromide below the 0.1 μ m and edge (below be called " dull and stereotyped particle of the present invention ") promptly, in all silver halide particle numbers, account for the photonasty silver emulsion more than 50% by not having year wheel construction and thickness.

Agi content in dull and stereotyped particle core of the present invention, preferably be in 1 mole of % above, 40 moles below the %, more preferably be in 1 mole of % above, 20 moles below the %, preferably be in 1 mole of % above, 10 moles below the %.

Dull and stereotyped particle of the present invention is characterized in that not observing a year wheel construction at above-mentioned core.A wheel construction was meant in so-called year, can observed year wheel pattern when utilizing common DJ (two injection) method to make dull and stereotyped particle growth, it is believed that it is the twin crystal dislocation that imports by the existence of iodide ion, and can on particle surface, form unnecessary electron trap.Year wheel construction can be observed by the line that is parallel to the particle limit.Year wheel construction can adopt the method identical with dislocation line observation described later to observe.

The dull and stereotyped particle surface of thin thickness is long-pending big as dull and stereotyped particle of the present invention, and efficient is extremely low so that above-mentioned the sort of twin crystal dislocation becomes in institute.

This dull and stereotyped particle that does not have year wheel construction can not adopt common DJ method to carry out particle growth, obtains but can adopt particulate to add growth method.Particulate adds growth method for example can open record in the flat 10-43570 communique with reference to the spy.

Dull and stereotyped particle of the present invention, its particle thickness are in below the 0.15 μ m, comprise ten above dislocation lines.Discoveries such as the inventor preferably make the core thickness attenuation if will improve the sensitivity of this particle.Under the thin situation of core thickness, can thicken shell thickness during same particle thickness.Because dislocation line is present in shell portion mostly, so shell portion is easy to make long dislocation line elongated when thick.Though be difficult to increase the bar number of dislocation line in the thin particle, it is believed that by increasing dislocation line to remedy this shortcoming.The core thickness of dull and stereotyped particle of the present invention is in below the 0.1 μ m, below the preferred 0.09 μ m, more preferably below the 0.08 μ m.

By axially cutting the ultra-thin section that dull and stereotyped particle obtains perpendicular to first type surface, can discern core and shell portion, and measure core thickness with transmission electron microscope observation.By on support, being coated with silver halide photographic emulsions, make the sample that dull and stereotyped particle and support are arranged in parallel substantially, and it is thick to utilize diamond cutter that it is cut into about 0.06 μ m, just can obtain ultra-thin section.

When utilizing transmission electron microscope observation to import the ultra-thin section of dull and stereotyped particle of dislocation line in the marginal portion, can observe four control lines with major surfaces in parallel usually.These control lines are divided into two lines and the close two inboard lines near particle surface.

Close two inboard line sources are in twin plane.Dull and stereotyped particle nearly all comprises the two sides twin plane, so can observe two corresponding with it lines.And under the situation that has three twin planes, can observe three corresponding with it lines.Can on ultra-thin section, observe five lines under this occasion.

Two line sources near first type surface make silver halide in the epitaxially grown operation of shell portion when importing dislocation.Agi content is than core particle height, mainly to be deposited on the condition growth of shell portion in the epitaxially grown silver halide.Even but under this condition, also can form the phase of a spot of high agi content in the first type surface part.The phase of this high agi content since it with on every side halogen form poor, can observe with linearity.That is to say, can will be decided to be core, will be decided to be shell portion near the particle surface side than its more close private side based on these two lines.

Among the present invention, dull and stereotyped particle has dislocation line.The dislocation line of dull and stereotyped particle for example can utilize and be documented in J.F.Hamilton, Phot.Sci.Eng., 11,57 (1967) and T.Shiozawa, J.Soc.Phot.Sci.Japan, on 35,213 (1972), use the direct observational method of transmission electron microscope to observe at low temperatures.That is to say, the marginal not meaning makes institute's applied pressure be unlikely the situation bottom that produces dislocation line on particle and takes out silver halide particle from emulsion, and it is online that it is stated from electron microscope observation usefulness, sample is being cooled to prevent to utilize transmission beam method to observe because of electron ray produces under the state of damage (printout etc.).Particle thickness this moment primary electron ray difficult seeing through more just more is so can more clearly observe when adopting high-pressure type (to the particle of 0.25 μ m thickness, accelerating potential is more than 200kV) electron microscope.By the particle photo that obtains by this method, can obtain position and bar number about the dislocation line of each particle when the direction vertical with first type surface observed.

In the silver halide particle of the present invention, in all silver halide particle numbers, account for dull and stereotyped particle more than 50% and have dislocation line more than 10.Preferably have 20 above dislocation lines, 30 above dislocation lines are more preferably arranged.Under the occasion of the intensive existence of dislocation line, perhaps can observe under the situation of dislocation line intersection, can not clearly count the dislocation line number of clear each particle sometimes.Yet, even under this occasion, also can number clear nearly about 10,20,30, obviously can distinguish mutually with the situation that only has several.About the dislocation line average of each particle, obtain mean value after can counting the dislocation line number of 100 above particles.Sometimes also can determine dislocation line up to hundreds of.

Dislocation line for example can import near the periphery of dull and stereotyped particle.The dislocation line of this situation, substantially vertical with periphery, begin to periphery generation dislocation line from position by the x% of the distance between dull and stereotyped particle center to the limit (periphery).This x value is preferred more than 10 and be lower than 100, more preferably more than 30 and be lower than 99, most preferably more than 50 and be lower than 98.Connect the formed shape in position that this dislocation line begins this moment, similar to shape of particle, but but incomplete similarity, distortion sometimes.Such dislocation number can not be seen in the central area of particle.The direction of dislocation line is though cardinal principle often is snakelike or intersecting each other in (211) direction on crystallography.

In addition, can in the Zone Full of dull and stereotyped particle periphery, have substantially dislocation line uniformly, also can have dislocation line at the periphery local location.That is to say, be example with the dull and stereotyped particle of sexangle, and dislocation line both can only be limited near six summits, also can only limit dislocation line near a summit therein.Otherwise dislocation line can also only be limited to the limit part except that six summits.

In addition, also can form dislocation line along the zone that comprises two parallel first type surface centers in the dull and stereotyped particle.Form in the first type surface whole district under the occasion of dislocation line, the direction of dislocation line is when observing perpendicular to the direction of first type surface, usually cardinal principle (211) direction on the crystallography, but also be (110) direction or random formation sometimes, and the length of each dislocation line also is random, sometimes on first type surface, short-term can be observed, the long line that arrives at limit (periphery) can be observed sometimes.Dislocation line is straight line sometimes, is snakelike mostly.And it is intersecting each other under most occasions.

The position of dislocation line as mentioned above, both can be limited on the periphery, on the first type surface or on the local location, also can form with its array configuration.That is to say, can also exist simultaneously on the periphery and on the first type surface.

If will in dull and stereotyped particle, import dislocation line, can reach mutually by high silver iodide are set in particle inside.Under this occasion, also can high silver iodide zone be set discontinuously in mutually at high silver iodide.Specifically, the high silver iodide of particle inside can obtain mutually like this, high silver iodide phase are set after promptly preparing fundamental particle (core), with agi content mutually covering its outside mutually lower than high silver iodide.The agi content of the dull and stereotyped particle of core is than high silver iodide low in mutually, preferred 0～20 mole of %, more preferably 0～15 mole of %.

The high silver iodide of so-called particle inside are meant the silver halide solid solution that contains silver iodide mutually.As the preferred silver iodide of silver halide in this case, iodine silver bromide, chlorine iodine silver bromide, but more preferably silver iodide and iodine silver bromide (agi content of the silver halide mutually contained with respect to these high silver iodide is 10～40 moles of %).Optionally be positioned at for the high silver iodide phase that makes this particle inside (below be called inner high silver iodide phase) on any position of limit, angle, face of fundamental particle, should control formation condition and the inner high silver iodide formation condition mutually and the formation condition that covers the phase in its outside of fundamental particle.

As the formation condition of fundamental particle, the having or not of pAg (logarithm of concentration of silver ions inverse) and ag halide solvent, kind and amount, temperature are key factors.Be in below 8.5 by the pAg that makes fundamental particle when growth, preferred below 8, generate inner high silver iodide phase time in the back the high silver iodide phase selectivity in this inside is present near the summit of fundamental particle or on the face.On the other hand, the pAg by making fundamental particle when growth is more than 8.5, and preferably more than 9, the high silver iodide phase time in inside generating the back can make inner high silver iodide be present in mutually on the limit of fundamental particle.

The boundary value of these pAg is along with the having or not of temperature and ag halide solvent, kind and amount and change.For example use as ag halide solvent under the occasion of thiocyanates, the boundary value of these pAg moves to high value direction.As the pAg in when growth pAg during this fundamental particle growth ending particularly importantly.On the other hand, even the pAg during growth does not satisfy above-mentioned numerical value,, also can control the chosen position of inner high silver iodide phase by adjusting the also slaking of this pAg value in fundamental particle growth back.Adopt ammonia, amines, thiourea derivative, thiocyanate this moment is effective as ag halide solvent.The generation of inner high silver iodide phase can be adopted so-called conversion method.Have as this method, in the particle forming process, the solubleness that add to form the salt of silver ion forms the method for the little halogen ion of particle or particle surface halogen ion on every side constantly than this, and the addition of the halogen ion that solubleness is little among the present invention, long-pending with respect to this particle surface constantly, be preferably in certain more than the value.For example, in the particle forming process, add the above KI of certain value with respect to the surface area of this moment silver halide particle and be advisable.Specifically, preferably add 8.2 * 10 ^-5Iodide salt more than mole/square metre.

The generation method of preferred internal silver iodide phase is when interpolation contains the halide salts aqueous solution of iodide salt, adds the method for silver salt solution.

For example when adding the KI aqueous solution, utilize two gunitees to add silver nitrate aqueous solution.At this moment the interpolation time that begins of KI aqueous solution and silver nitrate aqueous solution and interpolation termination time, also stagger in front and back mutually.With respect to the KI aqueous solution, the interpolation mol ratio of silver nitrate aqueous solution is preferably more than 0.1, more preferably more than 0.5, particularly preferably in more than 1.With respect to the halogen ion in the system and the iodide ion of interpolation, the total addition level of silver nitrate aqueous solution (mole) also can reach the superfluous zone of silver.PAg when adding these halide solutions that contain iodide ion and silver salt solution with two gunitees preferably adds the prolongation of times along with two injections and reduces.Add pAg before the beginning preferably more than 6.5 below 13, more preferably more than 7.0 below 11.The pAg that adds when stopping preferably is in more than 6.5 with below 10.0.

When implementing above method, silver halide solubleness is very low in the mixed system is advisable.Therefore, the mixed system temperature that forms high silver iodide phase time preferably is in more than 30 ℃ below 80 ℃, more preferably is in more than 30 ℃ below 70 ℃.

The formation of inner in addition high silver iodide phase, the preferred mode of adding particulate silver iodide, particulate iodine silver bromide, particulate chlorosulfonylation silver or particulate chlorine iodine silver bromide that adopts is carried out.The preferred especially mode of interpolation particulate silver iodide that adopts is carried out.These particulates are the particle of size below 0.1 μ m more than the 0.01 μ m normally, also can use but have 0.01 μ m particle following or the above particle size of 0.1 μ m.About the preparation method of these particulate silver halides, can open flat 1-183417 communique with reference to the spy, with the 2-44335 communique, with the 1-183644 communique, with the 1-183645 communique, with 2-43534 communique and with the method for putting down in writing in the 2-43535 communique.By adding these particulate silver halides and making it slaking, inner high silver iodide phase can be set.When making particle dissolution, also can use above-mentioned ag halide solvent by slaking.These particulates that add do not need immediately all dissolvings to disappear, as long as dissolving disappears when final particle is finished.

The center of the sexangle that the position of inner high silver iodide phase is projected from particle etc. is measured, preferably exist scope to be in 5 moles more than the % and be less than 100 moles of % with respect to all silver amounts of particle, more preferably at 20 moles more than the % and be less than 90 moles of %, particularly preferably in 50 moles more than the % and be less than 90 moles of %.Form the silver halide amount of these inner high silver iodide phases, the silver amount of being converted into accounts for all 50 moles of silver amount below the % of particle, more preferably 20 moles below the %.Being meant the prescription value of making silver emulsion mutually about these high silver iodide, is not to measure the value that halogen is formed in the final particle with various analytical approachs.In final particle, inner high silver iodide disappear because of giving recrystallization in the shell process etc. through regular meeting, and above-mentioned silver-colored measuring all refers to its prescription value.

Therefore, though in final particle, with said method dislocation line is observed easily, but for the internal silver iodide phase that imports for the importing dislocation line,, therefore often can not pick out as clear and definite phase because borderline silver halide composition can change continuously.Halogen about the particle each several part is formed, and can confirm by combination X-ray diffraction method, EPMA (also being XMA sometimes) method (utilizing electron ray scanning silver halide particle to detect the method that silver halide is formed), ESCA (also being the XPS method sometimes) method methods such as (to the methods of carrying out beam split from the photoelectron that particle surface is emitted through shining X ray).

The agi content of the outside that covers inner high silver iodide phase in mutually, be lower than the agi content of high silver iodide phase, with respect to the outside of this covering mutually in contained silver halide amount, be preferably 0～30 mole of %, more preferably 0～20 mole of %, most preferably 0～10 mole of %.

Form to cover temperature, the desirable arbitrary value of pAg value of the outside phase time of inner high silver iodide phase, preferred temperature is more than 30 ℃ below 80 ℃, preferably more than 35 ℃ below 70 ℃.PAg is preferably more than 6.5 below 11.5.Sometimes use the above-mentioned ag halide solvent effect can be better, most preferred ag halide solvent be a thiocyanate.

In addition, as the additive method that imports dislocation line in dull and stereotyped particle, the spy that has that can be suitable for opens the method for the use iodide ion releasing agent of being put down in writing on the flat 6-11782 communique.

Also the method appropriate combination use with above-mentioned importing dislocation line of this method of importing dislocation line can be imported dislocation line thus.

When silver halide particle is implemented chemical sensitization,, just be difficult to each particle is implemented best sensitizing if the size between the particle etc. are inhomogeneous, thereby the decline of the sensitivity that can cause taking a picture.Consider this point, the diameter of equivalent circle and the thickness of the dull and stereotyped particle of silver halide of the present invention are preferably monodispersed.The coefficient of alteration of the diameter of equivalent circle of all particles in the silver halide particle of the present invention preferably is in below 40%, and is more preferably below 30%, preferred especially below 20%; The coefficient of alteration of all particles thickness is preferably below 20%.Here the coefficient of alteration of said diameter of equivalent circle, the standard deviation that is meant diameter of equivalent circle is divided by the average equivalent circular diameter and amplify numerical value after 100 times.The standard deviation that so-called thickness variation coefficient is meant thickness amplifies 100 times numerical value after divided by average thickness.

The twin plane of dull and stereotyped particle preferably is in below the 0.014 μ m at interval, more preferably below the 0.012 μ m.In addition, when forming edge dislocation type particle, the homogeneity of dull and stereotyped particle lateral parts can influence the homogeneity of interparticle edge dislocation, and is therefore extremely important.From this point, the twin plane of dull and stereotyped particle coefficient of alteration at interval preferably is in below 40%.More preferably below 30%.Here said edge dislocation type particle is meant when main surface side is observed dull and stereotyped particle to have the particle of dislocation line in its edge (limit) part.

With the dull and stereotyped particle of (111) face as first type surface, be sexangle, triangle usually or be in its middle crop triangular shaped, have symmetry three times.In its six limits, the ratio on long three limits and short three limits is decided to be long limit/minor face ratio.Wherein so-called crop triangle is meant, cuts off the shape on each summit of triangle.When forming edge dislocation type particle, and compare near the hex shape particle, near in the triangular shaped particle, the dislocation line density that can observe edge part diminishes.Long limit/the minor face of dull and stereotyped particle is than preferably approaching 1.The mean value of the long limit/minor face ratio of dull and stereotyped particle preferably is in below 1.6, more preferably below 1.3.

The dull and stereotyped particle that uses among the present invention can become oersted Wa Erte slaking growth operation to form by karyomorphism.Any operation in these operations all is important for the width that suppresses particle size distribution, but owing to be difficult in the back dwindles the Size Distribution that produces in the operation in the operation that keeps left width, so become to must be noted that in the process Size Distribution is broadened at initial karyomorphism.Become at karyomorphism that the important point is in the process, utilize two gunitees in reactant liquor, to add silver ion and bromide ion and the karyomorphism that makes it to produce precipitation becomes relation between time and the reaction solution temperature.The spy who proposes according to the vegetarian rattan opens the record in the clear 63-92942 communique, and for improving monodispersity, the temperature of reaction solution preferably was in 20～45 ℃ of scopes when karyomorphism became.In addition, the spy who proposes the Zola to open the preferred temperature of having introduced in the flat 2-222940 communique when forming nuclear be below 60 ℃.

For obtaining the thin and monodispersed dull and stereotyped particle of particle thickness, when forming, particle can append gelatin sometimes.As the gelatin that uses this moment, preferred use the special gelatin of opening the chemical modification of putting down in writing in flat 10-148897 communique and the flat 11-143002 communique of Te Kai (in the gelatin-NH ₂When carrying out chemical modification, imported the gelatin of two-COOH group at least again).This chemical modification gelatin is characterised in that, when the amino in the gelatin is carried out chemical modification, has imported two above carboxyls at least again, preferably uses through the trimellitic acid gelatin, also preferably uses amber acidifying gelatin.This gelatin preferably adds before the growth operation, more preferably adds immediately after just forming nuclear.Whole dispersion medium quality had been advisable more than 60% when addition formed with respect to particle, and are preferred more than 80%, particularly preferably in more than 90%.

There is no particular restriction with the composition of dull and stereotyped particle for the present invention, the dull and stereotyped particle of preferred iodine silver bromide or chlorine iodine silver bromide.

Preferred 8 moles below the % of silver chloride content, more preferably 3 moles of following or 0 mole of % of %.About agi content, because the coefficient of alteration of the particle size distribution of dull and stereotyped particle emulsion preferably is in below 30%, so agi content preferably is in 20 moles below the %.By reducing agi content, can easily reduce the coefficient of alteration of dull and stereotyped particle diameter of equivalent circle.

The coefficient of alteration of dull and stereotyped particle size is particularly preferably in below 20%, and agi content is in 10 moles and is advisable below the %.

Dull and stereotyped particle preferably has the silver iodide distributed architecture in particle.Under this occasion, the silver iodide distributed architecture can have dual structure, triplen, quadruple structure and multiplet more.

In the silver halide particle of Shi Yonging, the coefficient of alteration that agi content distributes between particle preferably is in below 20%, more preferably is in below 15%, especially preferably is in below 10% in the present invention.The coefficient of alteration that agi content distributes between the particle of silver halide particle adopts the photographic property poor contrast of its photosensitive material greater than under 20% the occasion, and sensitivity significantly reduces and not ideal during pressurization.

With regard to the manufacture method that is used for the silver halide particle of agi content narrowly distributing between particle of the present invention, may be used singly or in combin known any method, for example special method, the spy who opens disclosed interpolation particulate in the flat 1-183417 communique etc. opens the method for disclosed use iodide ion releasing agent in the flat 2-68538 communique etc.

By analyzing the single particle composition, can measure the agi content of single particle with X-ray microanalyzer.The coefficient of alteration that agi content distributes between particle, the standard deviation and the average silver iodide content of the silver halide content that be to use at least 100 of mensuration, preferred 200, obtains during the agi content of preferred especially 300 above emulsion particles, by relational expression:

The value of (standard deviation/average silver iodide content) * 100=coefficient of alteration definition.The mensuration of single particle agi content is documented in No. 147868 instructions of European patent.Have two kinds of situations of correlativity and no correlativity between the agi content Yi of single particle (mole %) and each particle equivalent bulb diameter Xi (μ m), not having correlativity is perfect condition.The formation of forming about particle silver halide of the present invention for example can be confirmed by combination X-ray diffraction method, EPMA (also being XMA sometimes) method (utilizing electron ray scanning silver halide particle to detect the method for silver halide composition), ESCA (also being the XPS method sometimes) method methods such as (to shining the method that the photoelectron of emitting from particle surface behind the X ray carries out beam split).When measuring agi content among the present invention, so-called particle surface is meant that there is the zone of the 5 nanometer degree of depth on about distance surface, and so-called particle inside is meant the zone except that above-mentioned surface.The halogen of this particle surface is formed, and can adopt common ESCA method to measure.

Also can be in the formation of particle, particle forms the back and before chemical sensitization, in the chemical sensitization or after the chemical sensitization silver emulsion of the present invention is implemented reduction sensitization.

As reduction sensitization, can select in silver emulsion to add in the method for the method of the method for reduction sensitization agent, the growth in the low pAg atmosphere of pAg1～7 that is called silver-colored slaking or slaking, the growth in the high pH atmosphere of pH8～11 that is called high pH slaking or slaking any, also can be with two or more said methods usefulness also.

The adding method of reduction sensitization agent, the preferably method of the meticulous adjusting reduction sensitization level of energy.

As the reduction sensitization agent, known for example have tin salt, ascorbic acid and derivant thereof, amine and polynary amine, hydrazine derivate, formamidine sulfinic acid, silane compound, a monoborane compound etc.Can from these known reduction sensitization agent, select in the reduction sensitization of the present invention to use, and can and use two or more compounds.As the preferred stannous chloride of reduction sensitization agent, thiourea dioxide, dimethylamine monoborane, ascorbic acid and derivant thereof.It is relevant that the addition of reduction sensitization agent and emulsion are created conditions, so be necessary to select addition, adds 10 with every mole of silver halide ^-7～10 ^-3Mole is suitable.

The reduction sensitization agent is dissolved in that the back adds in the organic solvents such as water or alcohols, glycols, ketone, ester class, amide-type in the particle growth process.Also can add in advance in the reaction vessel, but preferably add in the suitable period of particle growth.In addition, can also in advance the reduction sensitization agent be added in water soluble silver salt or the water-soluble alkali halide solution, make the silver halide particle precipitation with these aqueous solution again.In addition, no matter be that the growth fraction that is accompanied by particle adds the reduction sensitization agent solution, still long-time continuously the interpolation all is desirable method.

In the manufacturing process of emulsion of the present invention, the preferred oxygenant that uses silver.The oxygenant of so-called silver is meant the compound that can be converted into silver ion with the argent reaction.Useful especially is will be transformed into the compound of silver ion as the very small silver particles that accessory substance generated in the forming process of silver halide particle and in the chemical sensitization process.Wherein the silver ion of Sheng Chenging both can form the silver salt that silver halide, silver sulfide, silver selenide etc. are insoluble in water, also can form silver nitrate and so on silver salt soluble in water.The oxygenant of silver both can be an inorganics, also can be organism.As inorganic oxidizer ozone, hydrogen peroxide and addition product thereof (NaBO is for example arranged ₂H ₂O ₂3H ₂O, 2NaCO ₃3H ₂O ₂, Na ₄P ₂O ₇2H ₂O ₂, 2Na ₂SO ₄H ₂O ₂2H ₂O), peracid salt (K for example ₂S ₂O ₈, K ₂C ₂O ₆, K ₂P ₂O ₈), peroxide coordination compound (K for example ₂[Ti (O ₂) C ₂H ₄] 3H ₂O, 4K ₂SO ₄Ti (O ₂) OHSO ₄2H ₂O, Na ₃[VO (O ₂) (C ₂H ₄) ₂6H ₂O], permanganate (KMnO for example ₄), chromate (K for example ₂Cr ₂O ₇) wait oxysalt, iodine or bromine and so on halogen, cross halate (for example periodic acid potassium), high-valency metal salt (for example potassium ferrocyanide) and thiosulfonate etc.

In addition, as organic oxidizing agent, can enumerate organic peroxides such as quinones, peracetic acid and benzylhydroperoxide such as 1,4-benzoquinone, emit the compound (for example N-bromo-succinimide, toluene-sodium-sulfonchloramide, chloramine B) of reactive halogen etc.

Preferred oxygenant is organic oxidizing agents such as inorganic oxidizer such as ozone, hydrogen peroxide and addition product thereof, halogen, thiosulfonate and quinones among the present invention.

Preferred embodiment be and with above-mentioned reduction sensitization with silver oxygenant.Can adopt and use method, its opposite approach or the employing of implementing reduction sensitization behind the oxygenant to make both simultaneously and the method for depositing.These methods are applicable to the particle forming process, also are applicable to the chemical sensitization process.

Also can be in the forming process of silver halide emulsion particles of the present invention, particle forms before back and the chemical sensitization or in the chemical sensitization, to wherein adding metal complex.Also can be divided in addition for several times and adding.Yet the silver halide particle the most surperficial 1/2 that preferably makes the distance use by the silver amount contains more than 50% of metal complex total amount contained in the silver halide particle with in the interior layer.Also can the not layer of containing metal coordination compound be set than the more outer side of said containing metal coordination compound layer here.

These metal complexes also can water or the appropriate solvent dissolving after, when forming silver halide particle, directly add in the reaction solution, perhaps add to and form in the halide solution that silver halide particle uses, in the silver salt solution or in the solution in addition, finishing the formation of particle, and make system contain metal complex thus.In addition, also can make it to be deposited on other the silver halide particle, so that system contains these metal complexes by adding and dissolving the silver halide grains that contains metal complex in advance.

When adding these metal complexes, the pH in the reaction solution preferably makes pH be in more than 1 below 10, and pH is in more than 3 below 7.

Silver emulsion of the present invention is preferably used selenium sensitizing.

As the selenium sensitizer that can use in the present invention, can use over disclosed selenium compound in the publication.Usually, instability mode selenium compound and/or non-instability mode selenium compound be, by add the back at high temperature, preferably under the temperature more than 40 ℃, emulsion is stirred certain hour and uses.As the instability mode selenium compound, the compound of putting down in writing on the preferred communique such as use that special public clear 44-15748, special public clear 43-13489 number, spy open flat 4-25832 number.So-called non-instability mode selenium sensitizer is meant, do not having under the situation of nucleophilic reagent, the silver selenide amount that is generated when only adding non-instability mode selenium sensitizer is the material below 30% of the non-instability mode selenium sensitizer that added, the compound of putting down in writing on the communique such as can enumerate special public clear 46-4553 number, special public clear 52-34492 number, special public clear 52-34491 number.When using non-instability mode selenium sensitizer, preferably and use nucleophilic reagent.Can enumerate the spy as nucleophilic reagent and open the compound of being put down in writing in flat 9-15776 communique etc.

In the presence of ag halide solvent, carry out selenium sensitizing and can obtain better effect.

As being used in ag halide solvent of the present invention, for example can enumerate United States Patent (USP) No. 3271157, with No. 3531289, with No. 3574628, the spy opens clear 54-1019 number, with (a) organic sulfur ethers of putting down in writing in the 54-158917 communique, for example the spy opens clear 53-82408 number, with 55-77737 number, (b) thiourea derivative with the record of 55-2982 communique, (c) that the spy opens clear 53-144319 communique record has the ag halide solvent that is inserted in the thiocarbonyl between oxygen or sulphur atom and the nitrogen-atoms, be documented in the spy and open (d) imidazoles on the clear 54-100717 communique, (e) sulphite, (f) thiocyanates.

Particularly preferred ag halide solvent has, thiocyanates and tetramethyl thiourea.Employed in addition quantity of solvent is different because of kind, and for example preferred amounts is 1 * 10 at every mole of silver halide sometimes ^-4More than the mole and 1 * 10 ^-3Below the mole.

As the golden sensitizer that above-mentioned golden sensitizing is used, can use the gold quantivalency for+1 valency or+3 valencys, as the normally used gold compound of golden sensitizer.Can enumerate for example chloroaurate, potassium chloroaurate, gold trichloride, thiocyanic acid gold potassium, Potassium Tetraiodoaurate, four cyano auric acid, thiocyanic acid gold ammonium (ammonium aurothiocyanate), pyridine radicals gold trichloride, aurosulfo, Auric selenide as its typical example.The addition of gold sensitizer is different because of various conditions, is generally directed to 1 mole of silver halide 1 * 10 ^-7More than the mole and 5 * 10 ^-5Be advisable below the mole.

In the emulsion of the present invention, when chemical sensitization, also be advisable with sulphur sensitizing.

Sulphur sensitizing is normally by adding sulphur sensitizer and at high temperature, preferably under the temperature more than 40 ℃ emulsion stirred certain hour and finishes.

Can adopt known sulphur sensitizer in the above-mentioned sulphur sensitizing.For example can enumerate thiosulfate, allylthiourea, allyl group isosulfocyanate, cystine, to toluene thiosulfonate, rhodanine etc.In addition, also can use United States Patent (USP) No. 1574944, with No. 2410689, with No. 2278947, with No. 2728668, with No. 3501313, open clear 55-45016 number etc. the sulphur sensitizer of putting down in writing in communique and the instructions with No. 3656955, No. the 1422869th, Deutsche Bundespatent, special public clear 56-24937 number, spy.As long as the addition of sulphur sensitizer is enough to increase effectively the sensitivity of emulsion.There is variation in this amount in suitable scope under various conditions such as pH, temperature, silver halide particle size, but every mole of silver halide preferably adds 1 * 10 ^-7More than the mole, 5 * 10 ^-5Below the mole.

Photographic emulsion of the present invention is preferably by adopting methine pigment and other pigments finishing spectral sensitization, thereby brings into play effect of the present invention effectively.Operable pigment comprises cyanines pigment, merocyanine pigment, compound cyanines pigment, composite part anthocyanidin, holopolar cyanine dyes, half cyanines pigment, styryl pigment, hemioxonol deys.Useful especially pigment is the pigment that belongs to cyanines pigment, merocyanine pigment and composite part anthocyanidin.These pigments also can be to contain the pigment that is used in any ring in the cyanines pigment usually as alkaline heterocycle.Can enumerate pyrrolin Huan, oxazoline ring, thiazoline ring, pyrrole ring, oxazole ring, thiazole ring, selenazoles ring, imidazole ring, tetrazole ring, pyridine ring as this ring; These rings are gone up the ring that addition has the alicyclic hydrocarbon ring; And these rings are gone up the ring that addition has the aromatic hydrocarbon ring, i.e. indolenine ring, benzo indolenine ring, indole ring, benzoxazole ring, naphthoxazole ring, benzothiazole ring, naphthothiazoles ring, benzo selenazoles ring, benzimidazole ring, quinoline ring etc.Also substituting group can be arranged on the carbon atom of these rings.

In merocyanine pigment and composite part anthocyanidin, as ring with oxo methylene structure, can contain pyrazolin-5-one ring, thiohydantoin ring, 2-Liu Za oxazolidine-2,4-diketone ring, thiazolidine-2,5～6 element heterocycles nuclear of 4-diketone ring, rhodanine ring, thiobarbituric acid ring and so on.

These sensitizing coloring matters can use separately, also it can be used in combination, the combination of sensitizing coloring matter especially is usually used in the purpose of rich shade sensitizing, its typical example for example is documented in United States Patent (USP) No. 2688545, with No. 2977229, with No. 3397060, with No. 35220523, with No. 3527641, with No. 3617293, with No. 3628964, with No. 3666480, with No. 3672898, with No. 3679428, with No. 3703377, with No. 3769301, with No. 3814609, with No. 3837862, with No. 4026707, No. the 1344281st, BrP, wait each instructions No. 1507803 together, and special public clear 43-4936 number, with 53-12375 number, the spy opens clear 52-110618 number, with waiting for 52-109925 number among each communique.

In emulsion, also can contain the material that itself does not have the pigment of spectral sensitization effect or in fact do not absorb visible light simultaneously, promptly show the material of rich shade sensitizing with sensitizing coloring matter.

In emulsion, add the period of sensitizing coloring matter, can be in any stage of the emulsion preparation that is considered to useful so far.Prevailing after chemical sensitization is finished the coating before during in carry out.As putting down in writing in No. the 3628969th, United States Patent (USP) and same No. 4225666 instructions, can together add with chemical sensitizer, chemical sensitization and spectral sensitization are carried out simultaneously, also can open in the clear 58-113928 communique and put down in writing as the spy, before chemical sensitization, carry out, add before can also finishing in the generation of silver halide particle precipitation in addition, with the beginning spectral sensitization.In addition, also can described in No. 4225666 instructions of United States Patent (USP) these sensitizing coloring matters separately be added, that is, with a part of adding before chemical sensitization in these sensitizing coloring matters, remainder adds after chemical sensitization.Can also be according to disclosed method in No. 4183756 instructions of United States Patent (USP), add any period in the silver halide particle forming process.

With respect to every mole of silver halide, sensitizing coloring matter can use 4 * 10 ^-6～8 * 10 ^-3Mole.When the equivalent bulb diameter of average particle size contained in the silver emulsion is under the occasion of 0.2～1.2 μ m, use about 5 * 10 with respect to every mole of silver halide ^-5～2 * 10 ^-3Mole can be more effective.

By adding the iodine silver bromide particle of prepared beforehand when the chemical sensitization and make it dissolving, silver emulsion of the present invention can improve through the time photographic fog.Still preferably at initial interpolation iodine silver bromide and make it dissolving after, continue successively add sensitizing coloring matter and chemical sensitizer as long as in during chemical sensitization interpolation period.Agi content is lower than agi content on the fundamental particle surface in the employed iodine silver bromide particle, preferred pure silver bromide emulsion.The size of this iodine silver bromide particle is not just had special restriction as long as can dissolve fully, and convenient amount bulb diameter is preferably in below the 0.1 μ m, more preferably below 0.05 μ m.The addition of iodine silver bromide particle is different with the fundamental particle that uses, but is advisable with 0.005～5 mole of % with respect to 1 moles of silver basically, more preferably 0.1～1 mole of %.

For improving color reproduction, preferably with No. the 4663271st, United States Patent (USP), with No. 4705744, with No. 4707436 instructions and special open clear 62-160448 number, with the tool interlayer effect of putting down in writing in the 63-89850 communique, divide photo sensitivity to distribute to be different from main photographic layers such as BL, GL, RL give floor (CL), be arranged on around main photographic layer adjacent or its.

Silver halide colour photographic sensitive material of the present invention has protective seam.So-called protective seam is meant the layer that is provided with in the photographic layer face side coating farthest of distance support.Record in the Te Kaiping 5-34857 communique by reducing the protective seam thickness and can improve sharpness, and, can well be utilized because of the light scattering degree of dull and stereotyped particle is little.

But result of study finds out that used thickness is thinned under the occasion of the following tabular particle of 0.15 μ m, and the light scattering degree that is caused by particle can increase on the contrary.It is believed that, under this occasion when the sharpness angle is considered and with the two and improper, but it is investigated and use under the occasion of dull and stereotyped particle of the present invention, by with the protective seam combination of thin thickness, can reach high sensitivity and can suppress the reduction of sharpness.In the silver halide colour photographic sensitive material of the present invention, protective layer thickness preferably is in below the 3 μ m, more preferably 2～0.5 μ m.Protective seam is by under the occasion that constitutes more than two-layer, with the thickness sum of these layers as protective layer thickness.

The determining film thickness that comprises protective seam carries out by the following method.At first under the condition through damping on the two under 25 ℃ of temperature and 55% relative humidity, measure with commercially available contact elcometer (AnritsuElectric Co.Ltd.K-402 BSTAND), total film thickness with whole hydrophilic colloid layers of emulsion layer one side can be obtained by the thickness difference of removing from sample on the support that is coated with layer front and back.The mensuration that each tunic of multilayer silver-halide color photoelement is thick can be carried out the mode that section carries out macrophotography by using scanning electron microscope.Usually sample need be placed under the vacuum when measuring and measure, can not keep state, will lose moisture content and the lower material of boiling point in the sample, therefore can not correctly measure thickness sometimes through the sample of damping drying with scanning electron microscope.Attempted adopting the method for making samples such as freeze-drying for this reason, but still abundant inadequately.According to the mensuration that crossgraphy carried out of scanning electron microscope, can be as calculating the mensuration means that each layer thickness of dry sample is used according to the film thickness value that records by the contact film thickness gauge.

The preferred non-photosensitive particulate silver halide that uses among the present invention.Non-photosensitive particulate silver halide is a kind of in not sensitization when obtaining pattern exposure that the pigment image carries out, and when its development treatment nonvisualized in fact silver halide grains, preferably do not form photographic fog in advance.Bromide sliver content is 0～100 mole of % in the non-photosensitive particulate silver halide, can contain silver chloride and/or silver iodide in case of necessity.Preferably contain 0.5～10 mole of % silver iodide.The mean grain size of non-photosensitive particulate silver halide (the diameter of equivalent circle mean value of projected area) is preferably 0.01～0.5 μ m, more preferably 0.02～0.2 μ m.

Non-photosensitive particulate silver halide can adopt with common photonasty silver halide and prepare with quadrat method.Non-photosensitive particulate silver halide surface does not need optical sensibilization, nor needs spectral sensitization.But before it is added in coating fluid, preferred triazole type, azepine indenes (azaindene) class, benzothiazole drone class or the known stabilizing agent such as thiol compound or zinc compound of adding in advance.Contain in the layer at this particulate silver halide particle, can contain collargol.

The present invention can be applied in black and white photographic pape, black-and-white negative stock film, X ray film, general or film with colour negative film, magic lantern with or shooting with in the various color sensitive materials such as colour reversal film, colour-printing paper, colour positive and colour reversal paper.In addition, also among the film assembly applicable to the band lens of putting down in writing in the fair 2-32615 of spy number, real fair 3-39784 communique.

Be suitable for the support that the present invention uses, for example be documented in 28 pages of above-mentioned RD No.17643, with among the No.18716 from page left hurdle, 647 pages of right hurdles to 648 and with on 879 pages of No.307105.

Photosensitive material of the present invention preferably is provided with the hydrophilic colloid layer (being called backing layer) that the dry film thickness sum is 2～20 μ m having tossing about of emulsion layer side.This backing layer preferably contains above-mentioned light absorber, optical filtering pigment, ultraviolet light absorber, antistatic agent, solid film, bonding agent, plastifier, lubricant, coating additive, surfactant etc.The swelling rate of this backing layer is preferably 150～500%.

Photosensitive material of the present invention can be according to the 28-29 page or leaf that is documented in above-mentioned RD No.17643, carry out development treatment with 651 pages of left hurdles of No.18716 to right hurdle and with the common method on the 880-881 page or leaf of No.307105.

The following treating fluid used of the explanation colour negative that can use in the present invention.

The colour developing developer solution that can use in the present invention can adopt the spy to open～the 11 page of hurdle, lower-left of 1 row, the 9th page of upper right hurdle of flat 4-121739 communique 4 row and go up the compound of record.Particularly the colour developing development host under the occasion is handled in conduct rapidly, preferred 2-methyl-4-(N-ethyl-N-(2-hydroxyethyl) amido) aniline, 2-methyl-4-(N-ethyl-N-(3-hydroxypropyl) amido) aniline, 2-methyl-4-(N-ethyl-N-(4-hydroxybutyl) amino) aniline.

These colour developing development hosts preferably in every liter of (following also represent with L) colour developing developer solution are used 0.01～0.08 mole, and more preferably 0.015～0.06 mole, preferred especially 0.02～0.05 mole.In addition, in the additional liquid of colour developing developer solution, preferably make it to contain in advance 1.1～3 times colour developing development host of this concentration, especially preferably make it to contain 1.3～2.5 times.

As the permanent agent of the guarantor of colour developing developer solution, can be extensive use of azanol, but when requiring under the occasion of higher guarantor's perseverance, preferably have substituent hydroxylamine derivatives such as alkyl or hydroxy alkyl, sulfo group alkyl, carboxyalkyl, specifically preferred N, N-two (sulfo group ethyl) azanol, monomethyl azanol, dimethyl hydroxylamine, an ethyl azanol, diethyl hydroxylamine, N, N-two (carboxy ethyl) azanol.Preferred especially N in the above-mentioned substance, N-two (sulfo group ethyl) azanol.Though these also can with azanol and usefulness, preferred use one or more to replace azanols.

The preferred permanent agent of guarantor of using 0.02～0.2 mole in every liter, more preferably 0.03～0.15 mole, preferred especially 0.04～0.1 molar range.In addition, same with the situation of colour developing development host in replenishing liquid, preferably contain the permanent agent of 1.1～3 times guarantor of mother liquor (liquid in the treatment trough) concentration.

Can use sulphite to prevent agent in the colour developing developer solution as the coking of colour developing development host oxide.Preferably, more preferably use with 0.02～0.04 molar range to use sulphite in every liter 0.01～0.05 molar range.Replenish preferred 1.1～3 times concentration use in the liquid with these.

In addition, the pH of colour developing developer solution is preferably 9.8～11.0, preferred especially 10.0～10.5.And preferably set to such an extent that exceed 0.1～1.0 in advance in the additional liquid than these numerical value.In order stably to keep this pH, can use known buffering agents such as carbonate, phosphate, sulfosalicylate, borate.

The magnitude of recruitment of colour developing developer solution is 80～1300 milliliters with respect to every square metre of photosensitive material preferably, but considers preferred addition amount scheme still less, specifically preferred 80～600 milliliters, more preferably 80～400 milliliters from the angle that alleviates the environmental pollution burden.

The bromide ion concentration of colour developing in the developer solution is generally 0.01～0.06 mole every liter, but from keeping sensitivity and suppress photographic fog improving discernment, and the purpose of improving graininess sets out, and preferably sets at 0.015～0.03 mole every liter.Bromide ion concentration is set under the occasion in this scope, can makes and replenish liquid and contain the bromide ion that is calculated as follows out.Wherein, when C in the following formula is negative value, preferably make additional liquid not contain bromide ion.

C＝A-W/V

C: the bromide ion concentration (mol/L) in the colour developing developer replenisher solution

A: bromide ion concentration (mol/L) in the target colour developing developer solution

W: make under the occasion that the colour developing of 1 square metre of photosensitive material develops the bromide ion amount (mol) of stripping in the colour developing developer solution from photosensitive material

V: to the magnitude of recruitment (L) of the colour developing developer replenisher solution of 1 square metre of photosensitive material.

In addition, when reducing magnitude of recruitment or setting under the occasion of perbromide ion concentration, as the method that improves sensitivity, also preferably use with 1-phenyl-3-pyrazolidone and 1-phenyl-2-methyl-2-methylol-3-pyrazolidone pyrazolidine ketone as representative, and with 3,6-two sulfo-s-1,8-ethohexadiol are the development accelerants such as sulfide compound of representative.

The treating fluid that employed colour reversal film is used among the present invention below is described.

About the treating fluid that the colour reversal film is used, write up is in No. six～the 10 page of 5 row of (on April 1st, 1991) the 1st page of 5 row of known technology and～the 24 page of 2 row of the 15th page of 8 row of the distribution of ァズテッ Network company limited, and these contents can both preferably adopt.

The photograph adjuvant that can use in the present invention is documented among the research disk roger (RD), has expressed relevant position below.

Additive types RD17643 RD18716 RD307105 number

1. 23 pages 648 pages right hurdles of chemical sensitizer are 866 pages

2. improve 648 pages of right hurdles of sensitivity agent

3. spectral sensitizer, 23～24 pages 648 pages right hurdles are 866～868 pages

Page right hurdle, rich shade sensitizer～649

4. 24 pages 647 pages right hurdles of whitening agent are 868 pages

5. light absorber, 25～26 pages 649 pages right hurdles are 873 pages

The optical filtering pigment ,～650 pages of left hurdles

Ultraviolet light absorber

6. 26 pages 651 pages left hurdles of bonding agent are 873～874 pages

7. plastifier, 27 pages 650 pages right hurdles are 876 pages

Lubricant

8. coating additive, 26～27 pages 650 pages right hurdles are 875～876 pages

Surfactant

9. 27 pages 650 pages right hurdles of antistatic agent are 876～877 pages

10. matting agent is 878～879 pages

Form functional colour former, various adjuvants etc. and development treatment such as colour former (coupler), DIR colour former about technology such as layer arrangements etc., silver emulsion, the pigment that can in silver halide photographic sensitive material of the present invention, use, be documented in european patent application and disclose 0565096A1 number (on October 13rd, 1993 disclosed) instructions and quote in the patent in this literary composition.Below list projects and corresponding with it record position respectively.

The layer structure: 61 page of 23～35 row ,～62 page of 14 row of 61 page of 41 row

2. middle layer: 61 page of 36～40 row

3. the interlayer effect is given layer: 62 page of 15～18 row

4. the silver halide halogen is formed: 62 page of 21～25 row

5. silver halide particle crystal habit: 62 page of 26～30 row

6. silver halide particle size: 62 page of 31～34 row

7. emulsion manufacture method: 62 page of 35～40 row

8. silver halide particle Size Distribution: 62 page of 41～42 row

9. lithographic plate particle: 62 page of 43～46 row

10. the inner structure of particle: 62 page of 47～53 row

11. the formation type of emulsion latent image: 62 pages 54～63 pages 5 row

12. the physics slaking of emulsion and chemical slaking: 63 page of 6～9 row

13. the mixing of emulsion is used: 63 page of 10～13 row

14.Fogged emulsions:63 page or leaf 14～31 row

15. non-photosensitive emulsion: 63 page of 32～43 row

16. silver coating amount: 63 page of 49～50 row

17. formaldehyde removes agent: 63 page of 54～57 row

18. being photographic fog, sulfydryl prevents agent: 65 page of 1～2 row

19.fogging releasing agents such as agent: 65 page of 3～7 row

20. pigment: 65 page of 7～10 row

21. all colored hair toners: 65 page of 11～13 row

22. yellow, magenta and cyan colour former: 65 page of 14～25 row

23. polymkeric substance colour former: 65 page of 26～28 row

24. the diffusivity pigment forms colour former: 65 page of 29～31 row

25. coloured colour former: 65 page of 32～38 row

26. overall function colour former: 65 page of 39～44 row

27. emit the bleach boosters colour former: 65 page of 45～48 row

28. emit the development accelerant colour former: 65 page of 49～53 row

29. other DIR colour formers :～66 page of 4 row of 65 page of 54 row

30. colour former process for dispersing: 66 page of 5～28 row

31. antiseptic and mildewproof agent: 66 page of 29～33 row

32. the kind of photosensitive material; 66 page of 34～36 row

33. photographic layer thickness and swelling speed :～67 page of 1 row of 66 page of 40 row

34. backing layer: 67 page of 3～8 row

35. whole development treatment: 67 page of 9～11 row

36. developer solution and developer: 67 page of 12～30 row

37. developer solution adjuvant: 67 page of 31～44 row

38. counter-rotating is handled: 67 page of 45～56 row

39. treating fluid numerical aperture (processing solution aperture ratio):

～68 page of 12 row of 67 page of 57 row

40. development time: 68 page of 13～15 row

41. blix, bleaching, photographic fixing :～69 page of 31 row of 68 page of 16 row

42. automatic processing machine: 69 page of 32～40 row

43. washing, rinsing and stabilization :～70 page of 18 row of 69 page of 41 row

44. the replenishing and re-using for the treatment of fluid: 70 page of 19～23 row

45. in the photosensitive material of development reagent is housed: 70 page of 24～33 row

46. development treatment temperature: 70 page of 34～38 row

47. the utilization to band lens film: 70 page of 39～41 row.

In addition, technology and the utilizations of the present invention on senior (advanced) photosensitive system such as the bleaching liquid that can use in silver halide photographic sensitive material of the present invention, magnetic recording layer, polyester support, antistatic agent are in (on April 11st, the 2002 open) instructions that is documented in U.S. Patent Application Publication 2002/0042030A1 number and the patent that is cited.Below list projects and corresponding therewith record position respectively.

1. bleaching liquid: 15 pages [0206]

2. magnetic recording layer and magnetic-particle: 16 pages [0207]～[0213]

3. polyester support: 16 pages of [0214]～17 page [0218]

4. antistatic agent: 17 pages [0219]～[0221]

5. lubricant: 17 pages [0222]

6. matting agent: 17 pages [0224]

7. film cassette: 17 pages of [0225]～18 page [0227]

8. to the utilization of feeling of high class photosystem: 18 pages [0228], [0238]～[0240]

9. to the utilization of being with the lens film: 18 pages [0229]

10. use the processing of microscale experiment system: 18 pages [0230]～[0237]

[embodiment]

Below utilize embodiment to specify the present invention.But the present invention is not subjected to any restriction of these embodiment.

(embodiment 1)

Support

The support that present embodiment is used is in order to the below manufactured.

1) the 1st layer and undercoat

To the poly-two sides to the (ethylene naphthalate) support of thickness 90 μ m, implemented the glow discharge of following condition and handled: the processing atmosphere pressures is H in 2.66 * 10Pa, the atmosphere gas ₂The dividing potential drop of O is 75%, discharge frequency is that 30KHz, output power are 2500 watts, to handle intensity be 0.5kVA minute/square metre.Adopt the rod of special public clear 58-4589 communique record to be coated with method, the coating fluid that will descend note to form with 5 milliliters of/square metre coating weights is coated on this support as the 1st layer.

Electrically conductive microparticle dispersion liquid (SnO ₂/ Sb ₂O ₅Particle concentration 50 weight portions

10% aqueous dispersions, initial size are 2 times of 005 μ m

Condensed matter, its mean grain size are 0.05 μ m)

Gelatin 0.5 weight portion

Water 49 weight portions

Polyglycereol polyglycidyl ether 0.16 weight portion

Poly-(degree of polymerization 20) oxygen ethene Span-20 0.1 weight portion

And then, after the 1st layer of coating, twist on the stainless-steel roll core of 20 centimetres of diameters, make it experience thermal process of 48 hours of heat treated under 110 ℃ of (Tg:119 of PEN support ℃) temperature, to carry out annealing in process, be coated with coating fluid that method will descend note to form with rod then and be coated on across the tossing about of the 1st layer of side of support with 10 milliliters of/square metre coating weights and go up the undercoat of using as emulsion.

Gelatin 1.01 weight portions

Salicylic acid 0.30 weight portion

Resorcinol 0.40 weight portion

Poly-(degree of polymerization 20) oxygen ethene nonylplenyl ether 0.11 weight portion

Water 3.53 weight portions

Methyl alcohol 84.57 weight portions

N-propanol 10.08 weight portions

Then be coated with layers 2 and 3 described later successively on the 1st layer, the colour negative photosensitive material by forming in the multiple layer coating of reverse side aftermentioned is made the transparent magnetic recording medium that has silver halide emulsion layer at last.

2) the 2nd layer (transparent magnetic recording layer)

(i) dispersion of magnetic

Add γ-Fe of the coating Co of 1100 weight portions ₂O ₃Magnetic (average major axis length: 0.25 micron, S _BET: 39m ²/ g, Hc:6.56 * 10 ⁴A/m, σ s:77.1Am ²/ kg, σ r:37.4Am ²/ kg), 220 weight parts waters and 165 weight portion silane coupling agents [3-(poly-(degree of polymerization 10) oxygen ethene) oxopropyl trimethoxy silane], fully mediated 3 hours with the open type kneader.After the adhesive liquid dried diel that under 70 ℃ this rough segmentation is loose removes and anhydrates,, made surperficial treated magnetic particle 110 ℃ of following heat treated 1 hour.

And then mediated 4 hours with the open type kneader again with following prescription.

Above-mentioned surface treated magnetic particle 855 grams

Diacetyl cellulose 25.3 grams

Methyl ethyl ketone 136.3 grams

Cyclohexanone 136.3 grams

Utilize sand mill (sand mill of 1/4G) following prescription fully to be disperseed 4 hours then with 2000rpm speed.Medium adopts the beaded glass of 1 millimeter of φ.

Above-mentioned liquid 45 grams that mix

Diacetyl cellulose 23.7 grams

Methyl ethyl ketone 127.7 grams

Cyclohexanone 127.7 grams

Make the intermediate liquid that contains magnetic by following prescription again.

(ii) contain the preparation of the intermediate liquid of magnetic

Fine dispersion liquid 674 grams of above-mentioned magnetic

Diacetyl cellulose solution 24280 grams

Gu (shape divides 4.34%, solvent: methyl ethyl ketone/cyclohexanone=1: 1)

Cyclohexanone 46 grams

These materials are mixed the back in decollator, stir, make " intermediate liquid that contains magnetic ".

Adopt following prescription to make Alpha-alumina abrasive substance dispersion liquid of the present invention.

(a) Sumikorandom AA-1.5 (average primary particle diameter 1.5 μ m, specific surface area 1.3 meters squared per gram)

The preparation of particle dispersion

Sumikorandom AA-1.5 152 grams

Silane coupling agent KBM903 (silicon Co., Ltd. of SHIN-ETSU HANTOTAI system) 0.48 gram

Diacetyl cellulose solution 227.52 grams

Gu (shape divides 4.5%, solvent: methyl ethyl ketone/cyclohexanone=1: 1)

Fully disperseed 4 hours by above-mentioned prescription with 800rpm speed with the sand mill (1/4G sand mill) that is coated with pottery.The medium that uses is the zirconium oxide bead of 1 millimeter of diameter.

(b) cataloid particle dispersion (fine particle)

" MEK-ST " that has used Misao Kusano to make.

It is that the average primary particle diameter of making dispersion medium with methyl ethyl ketone is the dispersion liquid of the cataloid of 0.015 μ m, Gu shape is divided into 30%.

The (iii) preparation of the 2nd layer of coating fluid

Intermediate liquid 19053 grams that contain above-mentioned magnetic

Diacetyl cellulose solution 264 grams

Gu (shape divides 4.5%, solvent: methyl ethyl ketone/cyclohexanone=1: 1)

Cataloid dispersion liquid " MEK-ST " [dispersion liquid b] 128 grams

(Gu shape is divided into 30%)

AA-1.5 dispersion liquid [dispersion liquid a] 12 grams

Millionate MR-400 (Japanese polyurethane (strain) system) dilution 203 grams

Gu (shape divides 20%, diluting solvent: methyl ethyl ketone/cyclohexanone=1: 1)

Methyl ethyl ketone 170 grams

Cyclohexanone 170 grams

Mix the coating fluid that the stirring above-mentioned substance forms with foundry pig (wire bar) coating, make coating weight reach 29.3 milliliters/square metre.Carry out drying under 110 ℃.Dried magnetic layer thickness is 1.0 μ m.

3) the 3rd layer (layer that contains the higher fatty acid ester lubricant)

(i) lubricant disperses the preparation of mother liquor

Note A liquid under 100 ℃ of following heating for dissolving disperses with high pressure homogenizer after adding B liquid to, has made lubricant and has disperseed mother liquor.A liquid

Under remember compound 399 weight portions

C ₆H ₁₃CH(OH)(CH ₂) ₁₀COOC ₅₀H ₁₀₁

Under remember compound 171 weight portions

n-C ₅₀H ₁₀₁O(CH ₂CH ₂O) ₁₆H

Cyclohexanone 830 weight portion B liquid

Cyclohexanone 8600 weight portions

The preparation of (ii) spherical inorganic particulate dispersion liquid

With following formulation spherical inorganic particulate dispersion liquid [c1].

Isopropyl alcohol 93.54 weight portions

Silane coupling agent KBM903 (silicon Co., Ltd. of SHIN-ETSU HANTOTAI system)

Compound 1-1:(CH ₃O) ₃Si-(CH ₂) ₃-NH ₂5.53 weight portion

Compound 1:2.93 weight portion

[changing 34]

Compound 1

SEAHOSTAR KEP50 88.00 weight portions

(Japanese catalyst (strain) is made for amorphism spherical silicon dioxide, mean grain size 0.5 μ m).

After 10 minutes, add following material by above-mentioned prescription stirring again.

Diacetone alcohol 252.93 weight portions

With the ice-cold stirring of aforesaid liquid,, made spherical inorganic particulate dispersion liquid c1 on one side on one side with ultrasonic homogenizer (SONIFIER450 (manufacturing of BRANSON company)) dispersion 3 hours.

The (iii) preparation of spherical organic macromolecule particle dispersion

According to following formulation spherical organic macromolecule particle dispersion [c2].

XC99-A8808 60 weight portions

(Kabushiki Kaisha Toshiba makes, spherical cross linking polysiloxane particle, mean grain size 0.9 μ m)

Methyl ethyl ketone 120 weight portions

Cyclohexanone 120 weight portions

Ice-cold stirring on one side, with ultrasonic homogenizer (SONIFIER450 (BRANSON company manufacturing)) disperse 2 hour on one side, spherical organic particle dispersion c2 made.

The (iv) preparation of the 3rd layer of coating fluid

Under above-mentioned lubricant disperses to add in the mother liquor, remember material, made the 3rd layer of coating fluid.

Diacetone alcohol 5950 grams

Cyclohexanone 176 grams

Ethyl acetate 1700 grams

Above-mentioned SEAHOSTAR KEP50 dispersion liquid [c1] 53.1 grams

Above-mentioned spherical organic macromolecule particle dispersion [c2] 300 grams

FC431 2.65 grams

(3M company makes, Gu shape divides 50%, and solvent: ethyl acetate)

BYK310 5.3 grams

(the chemical corporate system of BYK Japan is made, Gu shape is divided content 25%)

With 10.35 milliliters/square metre coating weights above-mentioned the 3rd layer of coating fluid is coated on the 2nd layer, through after 110 ℃ of dryings, again in 97 ℃ of dryings 3 minutes.

4) the coating setting of photographic layer

Then, be coated with each layer that plants the note composition, made colour negative at the multiple layer of tossing about of the above-mentioned backing layer that obtains.

(composition of photographic layer)

Corresponding to the numerical value of each composition, all expression represents to be converted into silver-colored coating weight with the gram/square metre coating weight of representing about silver halide.

(sample 101)

The 1st layer (the 1st anti-halo layer)

Black colloidal silver silver 0.074

Iodine silver bromide emulsion particle silver 0.010

(average equivalent bulb diameter 0.07 μ m, 2 moles of % of agi content)

Gelatin 0.740

ExM-1?????????????????????????????0.068

ExC-1?????????????????????????????0.002

ExC-3?????????????????????????????0.002

Cpd-2?????????????????????????????0.001

F-8???????????????????????????????0.001

HBS-1?????????????????????????????0.099

HBS-2?????????????????????????????0.013。

The 2nd layer (the 2nd anti-halo layer)

Black colloidal silver silver 0.094

Gelatin 0.667

ExF-1?????????????????????????????0.002

F-8???????????????????????????????0.001

Solid disperse dye EXF-7 0.100

HBS-1?????????????????????????????0.066

ExY-1?????????????????????????????0.039。

The 3rd layer (middle layer)

ExC-2?????????????????????????????0.050

Cpd-1?????????????????????????????0.089

Polyethyl acrylate latex 0.200

HBS-1?????????????????????????????0.054

Gelatin 0.458.

The 4th layer (the low red property of sensitivity sense emulsion layer)

Em-C silver 0.320

Em-D silver 0.414

ExC-1?????????????????????????????0.354

ExC-2?????????????????????????????0.014

ExC-3?????????????????????????????0.093

ExC-4????????????????????????????????????????????0.193

ExC-5????????????????????????????????????????????0.034

ExC-6????????????????????????????????????????????0.015

ExC-8????????????????????????????????????????????0.053

ExC-9????????????????????????????????????????????0.020

Cpd-2????????????????????????????????????????????0.025

Cpd-4????????????????????????????????????????????0.025

Cpd-7????????????????????????????????????????????0.015

UV-2?????????????????????????????????????????????0.022

UV-3?????????????????????????????????????????????0.042

UV-4?????????????????????????????????????????????0.009

UV-5?????????????????????????????????????????????0.075

HBS-1????????????????????????????????????????????0.274

HBS-5????????????????????????????????????????????0.038

Gelatin 2.757.

The 5th layer (the red property of middle sensitivity sense emulsion layer)

Em-B silver 1.152

ExM-5????????????????????????????????????????????0.011

ExC-1????????????????????????????????????????????0.304

ExC-2????????????????????????????????????????????0.057

ExC-3????????????????????????????????????????????0.020

ExC-4????????????????????????????????????????????0.135

ExC-5????????????????????????????????????????????0.012

ExC-6????????????????????????????????????????????0.039

ExC-8????????????????????????????????????????????0.016

ExC-9????????????????????????????????????????????0.077

Cpd-2????????????????????????????????????????????0.056

Cpd-4????????????????????????????????????????????0.035

Cpd-7????????????????????????????????????????????0.020

HBS-1??????????????????????????????????????????0.190

Gelatin 1.346.

The 6th layer (the red property of high sensitivity sense emulsion layer)

Em-A-1 silver 0.932

ExC-1??????????????????????????????????????????0.066

ExC-3??????????????????????????????????????????0.015

ExC-6??????????????????????????????????????????0.027

ExC-8??????????????????????????????????????????0.114

ExC-9??????????????????????????????????????????0.089

ExC-10?????????????????????????????????????????0.107

ExY-3??????????????????????????????????????????0.010

Cpd-2??????????????????????????????????????????0.070

Cpd-4??????????????????????????????????????????0.079

Cpd-7??????????????????????????????????????????0.030

HBS-1??????????????????????????????????????????0.314

HBS-2??????????????????????????????????????????0.120

Gelatin 1.206.

The 7th layer (middle layer)

Cpd-1??????????????????????????????????????????0.078

Cpd-6??????????????????????????????????????????0.369

Solid disperse dye ExF-4 0.030

HBS-1??????????????????????????????????????????0.048

Polyethyl acrylate latex 0.088

Gelatin 0.739

The 8th layer (giving the layer of interlayer effect) to feeling red property layer

Em-E silver 0.408

Cpd-4??????????????????????????????????????????0.034

ExM-2??????????????????????????????????????????0.121

ExM-3??????????????????????????????????????????0.002

ExM-4????????????????????????????????????????0.035

ExY-1????????????????????????????????????????0.018

ExY-4????????????????????????????????????????0.038

ExC-7????????????????????????????????????????0.036

HBS-1????????????????????????????????????????0.343

HBS-3????????????????????????????????????????0.006

HBS-5????????????????????????????????????????0.030

Gelatin 0.884.

The 9th layer (the low green property of sensitivity sense emulsion layer)

Em-H silver 0.276

Em-I silver 0.238

Em-J silver 0.325

ExM-2????????????????????????????????????????0.344

ExM-3????????????????????????????????????????0.055

ExY-1????????????????????????????????????????0.018

ExY-3????????????????????????????????????????0.014

ExC-7????????????????????????????????????????0.004

HBS-1????????????????????????????????????????0.505

HBS-3????????????????????????????????????????0.012

HBS-4????????????????????????????????????????0.095

HBS-5????????????????????????????????????????0.055

Cpd-5????????????????????????????????????????0.010

Cpd-7????????????????????????????????????????0.020

Gelatin 1.382.

The 10th layer (the green property of middle sensitivity sense emulsion layer)

Em-G silver 0.439

ExM-2????????????????????????????????????????0.046

ExM-3????????????????????????????????????????0.033

ExM-5????????????????????????????????????????0.019

ExY-3??????????????????????????????????????0.006

ExC-6??????????????????????????????????????0.010

ExC-7??????????????????????????????????????0.011

ExC-8??????????????????????????????????????0.010

ExC-9??????????????????????????????????????0.009

HBS-1??????????????????????????????????????0.046

HBS-3??????????????????????????????????????0.002

HBS-4??????????????????????????????????????0.035

HBS-5??????????????????????????????????????0.020

Cpd-5??????????????????????????????????????0.004

Cpd-7??????????????????????????????????????0.010

Gelatin 0.446.

11th layer (the green property of high sensitivity sense emulsion layer)

Em-F silver 0.497

Em-H silver 0.286

ExC-6??????????????????????????????????????0.007

ExC-8??????????????????????????????????????0.012

ExC-9??????????????????????????????????????0.014

ExM-1??????????????????????????????????????0.019

ExM-2??????????????????????????????????????0.056

ExM-3??????????????????????????????????????0.013

ExM-4??????????????????????????????????????0.034

ExM-5??????????????????????????????????????0.039

ExM-6??????????????????????????????????????0.021

ExY-3??????????????????????????????????????0.005

Cpd-3??????????????????????????????????????0.005

Cpd-4??????????????????????????????????????0.007

Cpd-5??????????????????????????????????????0.010

Cpd-7??????????????????????????????????????0.020

HBS-1??????????????????????????????????????????0.248

HBS-3??????????????????????????????????????????0.003

HBS-4??????????????????????????????????????????0.094

HBS-5??????????????????????????????????????????0.037

Polyethyl acrylate latex 0.099

Gelatin 0.950

The 12nd layer (Yellow filter layer)

Cpd-1??????????????????????????????????????????0.090

Solid disperse dye ExF-2 0.070

Solid disperse dye ExF-5 0.010

Oil-soluble dyes ExF-6 0.010

HBS-1??????????????????????????????????????????0.055

Gelatin 0.589

The 13rd layer (low sensitivity sense indigo plant emulsion layer)

Em-M silver 0.327

Em-N silver 0.174

Em-O silver 0.097

ExC-1????????????????????????????????????????0.006

ExC-3????????????????????????????????????????0.033

ExC-7????????????????????????????????????????0.014

ExY-1????????????????????????????????????????0.088

ExY-2????????????????????????????????????????0.404

ExY-4????????????????????????????????????????0.056

ExY-5????????????????????????????????????????0.404

Cpd-2????????????????????????????????????????0.102

Cpd-3????????????????????????????????????????0.004

HBS-1????????????????????????????????????????0.337

HBS-5????????????????????????????????????????0.070

Gelatin 1.876.

The 14th layer (high sensitivity sense indigo plant emulsion layer)

Em-L silver 0.421

Em-K silver 0.421

ExM-5??????????????????????????????????????0.012

ExC-1??????????????????????????????????????0.010

ExY-1??????????????????????????????????????0.041

ExY-2??????????????????????????????????????0.119

ExY-3??????????????????????????????????????0.008

ExY-4??????????????????????????????????????0.070

ExY-5??????????????????????????????????????0.120

Cpd-2??????????????????????????????????????0.074

Cpd-3??????????????????????????????????????0.001

Cpd-7??????????????????????????????????????0.030

HBS-1??????????????????????????????????????0.122

Gelatin 0.905.

The 15th layer (the 1st protective seam)

Iodine silver bromide emulsion particle silver 0.278

(average equivalent bulb diameter 0.07 μ m, 2 moles of % of agi content)

UV-1??????????????????????????????????????0.167

UV-2??????????????????????????????????????0.066

UV-3??????????????????????????????????????0.099

UV-4??????????????????????????????????????0.013

UV-5??????????????????????????????????????0.160

F-11??????????????????????????????????????0.008

S-1???????????????????????????????????????0.077

HBS-1?????????????????????????????????????0.175

HBS-4?????????????????????????????????????0.017

Gelatin 1.297.

The 16th layer (the 2nd protective seam)

H-1????????????????????????????????0.400

B-1 (diameter 1.7 μ m) 0.050

B-2 (diameter 1.7 μ m) 0.150

B-3????????????????????????????????0.029

S-1????????????????????????????????0.200

Gelatin 0.748.

In order to improve keeping quality, the property handled, resistance to pressure, the fungi-proofing property of mildew-resistant, antistatic behaviour and coating, can also make each layer suitably contain W-1～W-11, B-4～B-6, F-1～F-19 and lead salt, platinum salt, iridium salt, rhodium salt.

The organic solid disperse dyes disperse the preparation of thing

Disperseed the 12nd layer ExF-2 in order to following method.

2.800 kilograms of the wet cakes of ExF-2 (containing 17.6 weight % moisture content)

0.376 kilogram of octyl phenyl diethoxy methane-sulforic acid sodium salt

(31 weight % aqueous solution)

0.011 kilogram of F-15 (7% aqueous solution)

4.020 kilograms in water

Add up to 7.210 kilograms

(pH being adjusted to 7.2) with NaOH.

After the slurries that stir above-mentioned composition with high speed dispersor make it rough segmentation and loose, utilize LMK-4 type mixer grinder, be under 80% the condition at the filling rate of the discharge rate of the peripheral speed of 10 meter per seconds, 0.6 kg/min and 0.3 mm dia zirconium oxide bead, the delustring ratio that is distributed to dispersion liquid reaches till 0.29, has obtained solid disperse dye ExF-2.The mean grain size of dyestuff particulate is 0.29 μ m.

Utilization has obtained solid disperse dye ExF-4 and ExF-7 with quadrat method.The mean grain size of dyestuff particulate is respectively 0.28 μ m and 0.49 μ m.ExF-5 adopts european patent application to disclose little separating out (Microprecipitation) dispersion method of putting down in writing among the embodiment 1 of 549489A instructions to disperse.Mean grain size is 0.06 μ m.

Table 1 to table 4 shows the particle properties from Em-A-1 and Em-B to Em-O.Added the spectral sensitization pigment of record in the table 4 from Em-A-1 to Em-O with optimised quantity, golden sensitizing, sulphur sensitizing and selenium sensitizing have reached optimum efficiency.

Table 1

	Use layer	Shape of particle	Average equivalent bulb diameter (μ m)	Average equivalent circular diameter (μ m)/coefficient of alteration (%)	Average thickness (μ m)/coefficient of alteration (%)	The mean value of the diameter of equivalent circle of particle and the ratio of thickness	Dull and stereotyped particle proportion (%) in all particles number	The average thickness of core (μ m)	The average dislocation number of lines (bar) of each particle	A satisfies condition ^*Particle shared ratio (%) in all particles
	Use layer	Shape of particle	Average equivalent bulb diameter (μ m)		Average thickness (μ m)/coefficient of alteration (%)			The average thickness of core (μ m)			Em-A-1	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	??0.95	??1.95/28	??0.15/14	???13	????91	??0.12	????20	????25
?Em-B	Middle sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	??0.69	??1.14/35	??0.17/15	???6.7	????90	??0.12	????15	????35	Em-A-1	High sensitivity sense red beds		??0.95	??1.95/28	??0.15/14	???13	????91	??0.12	????20	????25
?Em-B	Middle sensitivity sense red beds		??0.69	??1.14/35	??0.17/15	???6.7	????90	??0.12	????15	????35	?Em-C	Low sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	??0.48	??0.89/17	??0.09/12	???10	????99	??0.07	????10	????10
?Em-D	Low sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	??0.31	??0.40/20	??0.09/9.3	???4.5	????98	??0.07	????10	????0	?Em-C	Low sensitivity sense red beds		??0.48	??0.89/17	??0.09/12	???10	????99	??0.07	????10	????10
?Em-D	Low sensitivity sense red beds		??0.31	??0.40/20	??0.09/9.3	???4.5	????98	??0.07	????10	????0	?Em-E	The sense red beds is given the layer of interlayer effect	(111) the dull and stereotyped particle of first type surface	??0.78	??1.38/30	??0.15/13	???9.2	????90	??0.12	????20	????35
?Em-F	The high sensitivity green layer	(111) the dull and stereotyped particle of first type surface	??1.00	??1.74/34	??0.22/16	???7.9	????91	??0.13	????20	????10	?Em-E	The sense red beds is given the layer of interlayer effect		??0.78	??1.38/30	??0.15/13	???9.2	????90	??0.12	????20	????35
?Em-F	The high sensitivity green layer		??1.00	??1.74/34	??0.22/16	???7.9	????91	??0.13	????20	????10	?Em-G	Middle sensitivity green layer	(111) the dull and stereotyped particle of first type surface	??0.74	??1.23/40	??0.18/18	???6.8	????90	??0.12	????15	????20
?Em-H	Height sensitivity green layer	(111) the dull and stereotyped particle of first type surface	??0.74	??1.39/25	??0.14/11	???9.9	????91	??0.12	????20	????15	?Em-G	Middle sensitivity green layer		??0.74	??1.23/40	??0.18/18	???6.8	????90	??0.12	????15	????20
?Em-H	Height sensitivity green layer		??0.74	??1.39/25	??0.14/11	???9.9	????91	??0.12	????20	????15	?Em-I	Low sensitivity green layer	(111) the dull and stereotyped particle of first type surface	??0.55	??0.79/30	??0.14/13	???5.5	????97	??0.13	????30	????0
?Em-J	Low sensitivity green layer	(111) the dull and stereotyped particle of first type surface	??0.44	??0.53/30	??0.17/18	???3.2	????97	??0.10	????20	????0	?Em-I	Low sensitivity green layer		??0.55	??0.79/30	??0.14/13	???5.5	????97	??0.13	????30	????0
?Em-J	Low sensitivity green layer		??0.44	??0.53/30	??0.17/18	???3.2	????97	??0.10	????20	????0	?Em-K	The blue layer of high sensitivity sense	(111) the dull and stereotyped particle of first type surface	??1.60	??3.00/25	??0.31/21	???10	????99	??0.16	????15	????0
?Em-L	The blue layer of high sensitivity sense	(111) the dull and stereotyped particle of first type surface	??1.30	??2.20/24	??0.34/22	???7	????98	??0.14	????20	????0	?Em-K	The blue layer of high sensitivity sense		??1.60	??3.00/25	??0.31/21	???10	????99	??0.16	????15	????0
?Em-L	The blue layer of high sensitivity sense		??1.30	??2.20/24	??0.34/22	???7	????98	??0.14	????20	????0	?Em-M	The blue layer of low sensitivity sense	(111) the dull and stereotyped particle of first type surface	??0.81	??1.10/30	??0.23/18	???4.7	????97	??0.13	????20	????5
?Em-N	The blue layer of low sensitivity sense	(111) the dull and stereotyped particle of first type surface	??0.40	??0.55/32	??0.13/16	???4.6	????96	??0.11	????20	????0	?Em-M	The blue layer of low sensitivity sense		??0.81	??1.10/30	??0.23/18	???4.7	????97	??0.13	????20	????5
?Em-N	The blue layer of low sensitivity sense		??0.40	??0.55/32	??0.13/16	???4.6	????96	??0.11	????20	????0	?Em-O	The blue layer of low sensitivity sense	(100) first type surface cube particle	??0.21	??0.21/20	??0.21/20	???1	????-	????-	????-	????-

^*Condition A: 1. by iodine silver bromide or chlorine iodine silver bromide form, 2. diameter of equivalent circle more than 1.0 μ m, thickness is below 0.15 μ m, 3. and, by not having year wheel construction and the core that forms by the iodine silver bromide below the thickness 0.1 μ m and have the shell portion of ten above dislocation lines to be constituted, and be the lithographic plate particle of first type surface with (111) face.

Table 2

	Use layer	Coefficient of alteration (%) between average silver iodide content (mole %)/particle	Surface agi content (%)	Coefficient of alteration (%) between average silver chloride content (mole %)/particle	Surface chlorination silver content (mole %)	Twin plane is (μ m)/coefficient of alteration (%) at interval	(100) face ratio in the side
	Use layer		Surface agi content (%)		Surface chlorination silver content (mole %)		(100) face ratio in the side	?Em-A-1	High sensitivity sense red beds	????4.5/10	????3.90	????0	????0	????0.011/30	????20
?Em-B	Middle sensitivity sense red beds	????5.5/11	????5.00	????0	????0	????0.010/30	????30	?Em-A-1	High sensitivity sense red beds	????4.5/10	????3.90	????0	????0	????0.011/30	????20
?Em-B	Middle sensitivity sense red beds	????5.5/11	????5.00	????0	????0	????0.010/30	????30	?Em-C	Low sensitivity sense red beds	????1.5/10	????3.70	????4.7/8.0	????16	????0.010/31	????25
?Em-D	Low sensitivity sense red beds	????1.1/11	????5.00	????12/9.0	????23	????0.009/29	????25	?Em-C	Low sensitivity sense red beds	????1.5/10	????3.70	????4.7/8.0	????16	????0.010/31	????25
?Em-D	Low sensitivity sense red beds	????1.1/11	????5.00	????12/9.0	????23	????0.009/29	????25	?Em-E	The sense red beds is given the layer of interlayer effect	????5.3/10	????5.90	????0	????0	????0.012/30	????35
?Em-F	The high sensitivity green layer	????5.1/10	????3.90	????0	????0	????0.012/30	????20	?Em-E	The sense red beds is given the layer of interlayer effect	????5.3/10	????5.90	????0	????0	????0.012/30	????35
?Em-F	The high sensitivity green layer	????5.1/10	????3.90	????0	????0	????0.012/30	????20	?Em-G	Middle sensitivity green layer	????6.5/13	????5.60	????0	????0	????0.010/30	????30
?Em-H	Height sensitivity green layer	????5.3/14	????5.97	????0	????0	????0.011/30	????30	?Em-G	Middle sensitivity green layer	????6.5/13	????5.60	????0	????0	????0.010/30	????30
?Em-H	Height sensitivity green layer	????5.3/14	????5.97	????0	????0	????0.011/30	????30	?Em-I	Low sensitivity green layer	????6.3/12	????7.39	????0	????0	????0.016/32	????20
?Em-J	Low sensitivity green layer	????2.0/14	????5.68	????0	????0	????0.016/32	????35	?Em-I	Low sensitivity green layer	????6.3/12	????7.39	????0	????0	????0.016/32	????20
?Em-J	Low sensitivity green layer	????2.0/14	????5.68	????0	????0	????0.016/32	????35	?Em-K	The blue layer of high sensitivity sense	????5.8/7.0	????3.88	????0	????0	????0.010/29	????40
?Em-L	The blue layer of high sensitivity sense	????6.1/8.0	????5.50	????0	????0	????0.017/33	????20	?Em-K	The blue layer of high sensitivity sense	????5.8/7.0	????3.88	????0	????0	????0.010/29	????40
?Em-L	The blue layer of high sensitivity sense	????6.1/8.0	????5.50	????0	????0	????0.017/33	????20	?Em-M	The blue layer of low sensitivity sense	????6.3/9.0	????1.90	????0	????0	????0.019/30	????30
?Em-N	The blue layer of low sensitivity sense	????4.0/10	????5.50	????0	????0	????0.020/31	????30	?Em-M	The blue layer of low sensitivity sense	????6.3/9.0	????1.90	????0	????0	????0.019/30	????30
?Em-N	The blue layer of low sensitivity sense	????4.0/10	????5.50	????0	????0	????0.020/31	????30	?Em-O	The blue layer of low sensitivity sense	????3.8/9.0	????4.50	????0	????0	????-	????-

Table 3

	Use layer	Account for the feature of the particle more than 70% of full projected area	In the particle configuration silver-colored amount ratio (%) and halogen form (beginning record) from the particle center＜in be the extension junction surface
	Use layer			?Em-A-1	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	(11％)AgBr/(35％)AgBr ₉₇I ₃/(18％)AgBr/(9％)AgBr ₆₂I ₃₈/(27％)AgBr
?Em-B	Middle sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	(7％)AgBr/(31％)AgBr ₉₇I ₃/(16％)AgBr/(12％)AgBr ₆₂I ₃₈/(34％)AgBr	?Em-A-1	High sensitivity sense red beds
?Em-B	Middle sensitivity sense red beds			?Em-C	Low sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	(1％)AgBr/(77％)AgBr ₉₉I ₁/(9％)AgBr ₉₅I ₅/(13％)<AgBr ₆₃Cl ₃₅I ₂>
?Em-D	Low sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	(57％)AgBr/(14％)AgBr ₉₆I ₄/(29％)<AgBr ₅₇Cl ₄₁I ₂>	?Em-C	Low sensitivity sense red beds
?Em-D	Low sensitivity sense red beds		(57％)AgBr/(14％)AgBr ₉₆I ₄/(29％)<AgBr ₅₇Cl ₄₁I ₂>	?Em-E	The sense red beds is given the layer of interlayer effect	(111) the dull and stereotyped particle of first type surface	(13％)AgBr/(36％)AgBr ₉₇I ₃/(7％)AgBr/(11％)AgBr ₆₂I ₃₈/(33％)AgBr
?Em-F	The high sensitivity green layer	(111) the dull and stereotyped particle of first type surface	(11％)AgBr/(35％)AgBr ₉₇I ₃/(18％)AgBr/(4％)AgI/(32％)AgBr	?Em-E	The sense red beds is given the layer of interlayer effect
?Em-F	The high sensitivity green layer		(11％)AgBr/(35％)AgBr ₉₇I ₃/(18％)AgBr/(4％)AgI/(32％)AgBr	?Em-G	Middle sensitivity green layer	(111) the dull and stereotyped particle of first type surface	(7％)AgBr/(31％)AgBr ₉₇I ₃/(15％)AgBr/(14％)AgBr ₆₂I ₃₈/(33％)AgBr
?Em-H	Height sensitivity green layer	(111) the dull and stereotyped particle of first type surface	(14％)AgBr/(36％)AgBr ₉₇I ₃/(7％)AgBr/(11％)AgBr ₆₂I ₃₈/(32％)AgBr	?Em-G	Middle sensitivity green layer
?Em-H	Height sensitivity green layer			?Em-I	Low sensitivity green layer	(111) the dull and stereotyped particle of first type surface	(15％)AgBr/(44％)AgBr ₉₇I ₃/(11％)AgBr/(5％)AgI/(25％)AgBr
?Em-J	Low sensitivity green layer	(111) the dull and stereotyped particle of first type surface	(60％)AgBr/(2％)AgI/(38％)AgBr	?Em-I	Low sensitivity green layer		(15％)AgBr/(44％)AgBr ₉₇I ₃/(11％)AgBr/(5％)AgI/(25％)AgBr
?Em-J	Low sensitivity green layer		(60％)AgBr/(2％)AgI/(38％)AgBr	?Em-K	The blue layer of high sensitivity sense	(111) the dull and stereotyped particle of first type surface	(68％)AgBr ₉₃I ₇/(21％)AgBr/(1％)AgI/(10％)AgBr
?Em-L	The blue layer of high sensitivity sense	(111) the dull and stereotyped particle of first type surface	(8％)AgBr/(10％)AgBr ₉₅I ₅/(52％)AgBr ₉₃I ₇/(11％)AgBr/(2％)AgI/(17％)AgBr	?Em-K	The blue layer of high sensitivity sense		(68％)AgBr ₉₃I ₇/(21％)AgBr/(1％)AgI/(10％)AgBr
?Em-L	The blue layer of high sensitivity sense			?Em-M	The blue layer of low sensitivity sense	(111) the dull and stereotyped particle of first type surface	(12％)AgBr/(43％)AgBr ₉₀I ₁₀/(14％)AgBr/(2％)AgI/(29％)AgBr
?Em-N	The blue layer of low sensitivity sense	(111) the dull and stereotyped particle of first type surface	(58％)AgBr/(4％)AgI/(38％)AgBr	?Em-M	The blue layer of low sensitivity sense		(12％)AgBr/(43％)AgBr ₉₀I ₁₀/(14％)AgBr/(2％)AgI/(29％)AgBr
?Em-N	The blue layer of low sensitivity sense		(58％)AgBr/(4％)AgI/(38％)AgBr	?Em-O	The blue layer of low sensitivity sense	(100) first type surface cube particle	(6％)AgBr/(94％)AgBr ₉₆I ₄

Table 4

	Use layer	Sensitizing coloring matter	Alloy
	Use layer	Sensitizing coloring matter	Alloy	Em-A-1	High sensitivity sense red beds	1，3，4	?K ₂IrCl ₆，K ₄Fe(CN) ₆
?Em-B	Middle sensitivity sense red beds	2，3，4	?K ₂IrCl ₆，K ₂IrCl ₅(H ₂₀)，K ₄Ru(CN) ₆	Em-A-1	High sensitivity sense red beds	1，3，4	?K ₂IrCl ₆，K ₄Fe(CN) ₆
?Em-B	Middle sensitivity sense red beds	2，3，4	?K ₂IrCl ₆，K ₂IrCl ₅(H ₂₀)，K ₄Ru(CN) ₆	?Em-C	Low sensitivity sense red beds	1，3，4	?K ₂IrCl ₆，K ₄Fe(CN) ₆
?Em-D	Low sensitivity sense red beds	1，3，4	?K ₂IrCl ₆，K ₄Fe(CN) ₆	?Em-C	Low sensitivity sense red beds	1，3，4	?K ₂IrCl ₆，K ₄Fe(CN) ₆
?Em-D	Low sensitivity sense red beds	1，3，4	?K ₂IrCl ₆，K ₄Fe(CN) ₆	?Em-E	The sense red beds is given the layer of interlayer effect	5，10	?K ₄Fe(CN) ₆
?Em-F	The high sensitivity green layer	5，6，9	?K ₄Ru(CN) ₆	?Em-E	The sense red beds is given the layer of interlayer effect	5，10	?K ₄Fe(CN) ₆
?Em-F	The high sensitivity green layer	5，6，9	?K ₄Ru(CN) ₆	?Em-G	Middle sensitivity green layer	5，6，9	?K ₂IrCl ₆，K ₄Fe(CN) ₆
?Em-H	Height sensitivity green layer	5，6，7，8，9	?K ₂IrCl ₆，K ₄Fe(CN) ₆	?Em-G	Middle sensitivity green layer	5，6，9	?K ₂IrCl ₆，K ₄Fe(CN) ₆
?Em-H	Height sensitivity green layer	5，6，7，8，9	?K ₂IrCl ₆，K ₄Fe(CN) ₆	?Em-I	Low sensitivity green layer	6，8，9	?K ₂IrCl ₆
?Em-J	Low sensitivity green layer	5，6，7	?K ₂IrCl ₆，K ₄Fe(CN) ₆	?Em-I	Low sensitivity green layer	6，8，9	?K ₂IrCl ₆
?Em-J	Low sensitivity green layer	5，6，7	?K ₂IrCl ₆，K ₄Fe(CN) ₆	?Em-K	The blue layer of high sensitivity sense	14	?-
?Em-L	The blue layer of high sensitivity sense	12	?-	?Em-K	The blue layer of high sensitivity sense	14	?-
?Em-L	The blue layer of high sensitivity sense	12	?-	?Em-M	The blue layer of low sensitivity sense	14	?-
?Em-N	The blue layer of low sensitivity sense	12，13	?-	?Em-M	The blue layer of low sensitivity sense	14	?-
?Em-N	The blue layer of low sensitivity sense	12，13	?-	?Em-O	The blue layer of low sensitivity sense	11，13	?K ₂IrCl ₆

The sensitizing coloring matter of record is expressed as follows in the table 4.

[changing 35]

Sensitizing coloring matter 1

[changing 36]

Sensitizing coloring matter 2

[changing 37]

Sensitizing coloring matter 3

[changing 38]

Sensitizing coloring matter 4

[changing 39]

Sensitizing coloring matter 5

[changing 40]

Sensitizing coloring matter 6

[changing 41]

Sensitizing coloring matter 7

[changing 42]

Sensitizing coloring matter 8

[changing 43]

Sensitizing coloring matter 9

[changing 44]

Sensitizing coloring matter 10

[changing 45]

Sensitizing coloring matter 11

[changing 46]

Sensitizing coloring matter 12

[changing 47]

Sensitizing coloring matter 13

[changing 48]

Sensitizing coloring matter 14

The preparation of tabular particle is the embodiment that opens flat 1-158426 communique record according to the spy, uses low molecular weight gelatine to carry out.

Be reduced sensitizing during Em-K～N particle preparation.

Em-H is the embodiment that opens flat 6-11782 communique record according to the spy, uses iodide ion to emit agent and import dislocation.

Be recorded in the spy and open the silver iodide particulate of adjusting in another chamber of the magnetic coupling induction type stirring machine in the flat 10-43570 communique and import dislocation having before Em-E is to use and adds.

The compound of below representing each layer usefulness.

[changing 49]

[changing 50]

[changing 51]

[changing 52]

[changing 53]

[changing 54]

[changing 55-1]

[changing 55-2]

[changing 56]

[changing 57]

[changing 58]

X/y=10/90 (mass ratio) mean molecular weight: about 35,000

X/y=40/60 (mass ratio) mean molecular weight: about 20,000

Mean molecular weight: about 750,000

X/y=70/30 (mass ratio) mean molecular weight: about 17,000

Mean molecular weight: about 10,000

[changing 59]

The HBS-1 phosphoric acid trimethylbenzene phenolic ester

The HBS-2 n-butyl phthalate

HBS-4 tricresyl phosphate (the 2-ethyl is own) ester

[changing 60]

[changing 61]

[changing 62]

x/y/z＝20/60/20

(mass ratio)

Mean molecular weight: about 36,000

With above-mentioned silver halide colour photographic sensitive material as sample 101.

(sample 102～113)

Emulsion Em-A-1 according to the 6th layer in table 5 change sample 101 adds compound of the present invention in the 6th layer according to table 5 again, has made sample 102～113 thus.The characteristic of emulsion Em-A-2～Em-A-6 is shown among the table 5.

Table 5-1

Sample	The emulsion name	Use layer	Shape of particle	Average equivalent bulb diameter (μ m)	Average equivalent circular diameter (μ m)/coefficient of alteration (%)	Average thickness (μ m)/coefficient of alteration (%)	The mean value of the diameter of equivalent circle of particle and the ratio of thickness	Dull and stereotyped particle accounts for the ratio (%) of all populations
Sample	The emulsion name	Use layer	Shape of particle	Average equivalent bulb diameter (μ m)		Average thickness (μ m)/coefficient of alteration (%)			?101	?Em-A-1	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????1.95/28	????0.15/14	????13	????97
?102	?Em-A-1	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????1.95/28	????0.15/14	????13	????97	?101	?Em-A-1	High sensitivity sense red beds		????0.95	????1.95/28	????0.15/14	????13	????97
?102	?Em-A-1	High sensitivity sense red beds		????0.95	????1.95/28	????0.15/14	????13	????97	?103	?Em-A-2	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????2.10/30	????0.13/14	????16	????97
?104	?Em-A-3	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????2.10/30	????0.13/14	????16	????97	?103	?Em-A-2	High sensitivity sense red beds		????0.95	????2.10/30	????0.13/14	????16	????97
?104	?Em-A-3	High sensitivity sense red beds		????0.95	????2.10/30	????0.13/14	????16	????97	?105	?Em-A-2	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????2.10/30	????0.13/14	????16	????97
?106	?Em-A-4	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????2.20/32	????0.12/14	????18	????97	?105	?Em-A-2	High sensitivity sense red beds		????0.95	????2.10/30	????0.13/14	????16	????97
?106	?Em-A-4	High sensitivity sense red beds		????0.95	????2.20/32	????0.12/14	????18	????97	?107	?Em-A-4	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????2.20/32	????0.12/14	????18	????97
?108	?Em-A-4	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????2.20/32	????0.12/14	????18	????97	?107	?Em-A-4	High sensitivity sense red beds		????0.95	????2.20/32	????0.12/14	????18	????97
?108	?Em-A-4	High sensitivity sense red beds		????0.95	????2.20/32	????0.12/14	????18	????97	?109	?Em-A-4	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????2.20/32	????0.12/14	????18	????97
?110	?Em-A-5	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????1.95/28	????0.15/14	????13	????97	?109	?Em-A-4	High sensitivity sense red beds		????0.95	????2.20/32	????0.12/14	????18	????97
?110	?Em-A-5	High sensitivity sense red beds		????0.95	????1.95/28	????0.15/14	????13	????97	?111	?Em-A-5	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????1.95/28	????0.15/14	????13	????97
?112	?Em-A-6	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????1.83/27	????0.17/14	????11	????97	?111	?Em-A-5	High sensitivity sense red beds		????0.95	????1.95/28	????0.15/14	????13	????97
?112	?Em-A-6	High sensitivity sense red beds		????0.95	????1.83/27	????0.17/14	????11	????97	?113	?Em-A-6	High sensitivity sense red beds	(111) the dull and stereotyped particle of first type surface	????0.95	????1.83/27	????0.17/14	????11	????97

Table 5-2

Sample	The average thickness of core (μ m)	The average dislocation number of lines (bar) of each particle	A satisfies condition ^*Particle shared ratio (%) in all particles	Compound (0.156g/m of the present invention ²)	Relative sensitivity	Graininess	Remarks
Sample	The average thickness of core (μ m)			Compound (0.156g/m of the present invention ²)	Relative sensitivity	Graininess	Remarks	??101	?????0.12	????20	????25	Do not have	????100	????100	Comparative example
??102	?????0.12	????20	????25	????HET3	????105	????100	Comparative example	??101	?????0.12	????20	????25	Do not have	????100	????100	Comparative example
??102	?????0.12	????20	????25	????HET3	????105	????100	Comparative example	??103	?????0.10	????20	????40	Do not have	????101	????100	Comparative example
??104	?????0.10	????5	????30	????HET3	????105	????101	Comparative example	??103	?????0.10	????20	????40	Do not have	????101	????100	Comparative example
??104	?????0.10	????5	????30	????HET3	????105	????101	Comparative example	??105	?????0.10	????20	????60	????HET3	????120	????99	The present invention
??106	?????0.09	????20	????80	????HET3	????130	????99	The present invention	??105	?????0.10	????20	????60	????HET3	????120	????99	The present invention
??106	?????0.09	????20	????80	????HET3	????130	????99	The present invention	??107	?????0.09	????20	????80	????(2)	????150	????99	The present invention
??108	?????0.09	????20	????80	????(59)	????160	????99	The present invention	??107	?????0.09	????20	????80	????(2)	????150	????99	The present invention
??108	?????0.09	????20	????80	????(59)	????160	????99	The present invention	??109	?????0.09	????20	????80	????(60)	????145	????99	The present invention
??110	?????0.10	????20	????50	Do not have	????100	????100	Comparative example	??109	?????0.09	????20	????80	????(60)	????145	????99	The present invention
??110	?????0.10	????20	????50	Do not have	????100	????100	Comparative example	??111	?????0.10	????20	????50	????HET3	????115	????99	The present invention
??112	?????0.10	????20	????40	Do not have	????97	????100	Comparative example	??111	?????0.10	????20	????50	????HET3	????115	????99	The present invention
??112	?????0.10	????20	????40	Do not have	????97	????100	Comparative example	??113	?????0.10	????20	????40	????HET3	????105	????99	Comparative example

The FP-360B type automatic processing machine that uses Fuji Photo Film Co., Ltd. to make during development carries out as follows.Wherein the overflowing liquid of bleaching bath does not flow to the back bath, is transformed into all to be discharged in the waste liquid tank.Carried the evaporation compensated mechanism of record in known skill and technique 94-4992 number (distribution of invention association of civic organization) on this FP-360B.

Treatment process and treating fluid composition are expressed as follows.

(treatment process)

Operation processing time treatment temperature magnitude of recruitment * tankage size

Colour developing develop 3 minutes 5 seconds 37.8 ℃ 20 milliliters 11.5 liters

Bleach 50 seconds 38.0 ℃ 5 milliliters 5 liters

38.0 ℃-5 liters of photographic fixing (1) 50 second

38.0 ℃ 8 milliliters 5 liters of photographic fixing (2) 50 seconds

Wash 30 seconds 38.0 ℃ 17 milliliters 3 liters

Stable (1) 20 second 38.0 ℃-3 liters

Stable (2) 20 seconds 38.0 ℃ 15 milliliters 3 liters

Dry 1 minute and 30 seconds 60.0 ℃

* magnitude of recruitment: 1.1 meters long photosensitive materials of per 3.5 mm wides (being equivalent to the 24Ex.1 volume)

Stabilizing solution and stop bath adopt from (2) reflux type to (1), and the overflowing liquid of washing water is all imported in the fixing bath (2).Wherein bring amount, bleaching liquid bring amount and stop bath the bring amount in washing step in photographic fixing operation of developer solution in bleaching process is respectively 2.5 milliliters, 2.0 milliliters and 2.0 milliliters for 1.1 meters long photosensitive materials of 35 mm wides.And transit time be 6 seconds, before this time comprises in processing time of operation.

The aperture area of above-mentioned processor is 100 square centimeters in the colour developing developer solution, is 120 square centimeters in bleaching liquid, is about 100 square centimeters in other treating fluids.

The composition for the treatment of fluid below is shown.

(colour developing developer solution) jar liquid (gram) replenishes liquid (gram)

Diethylene-triamine pentaacetic acid 3.0 3.0

Catechol-3,5-disulfonic acid disodium 0.3 0.3

Sodium sulphite 3.9 5.3

Sal tartari 39.0 39.0

Disodium-N, two (the 2-sulfonic acid ethyl ester) azanols 1.5 2.0 of N-

Potassium bromide 1.3 0.3

1.3 milligrams of potassium iodides-

4-hydroxyl-6-methyl isophthalic acid, 3,3a, the 7-purine 0.05-

(テトラザインデン)

Hydroxylamine sulfate 2.4 3.3

2-methyl-4-(N-ethyl-N-

(beta-hydroxyethyl) amido) aniline sulfate 4.5 6.5

Add water to 1.0 liters 1.0 liters

PH (with potassium hydroxide and sulfuric acid adjustment) 10.05 10.18.

(bleaching liquid) jar liquid (gram) replenishes liquid (gram)

1,3-diaminopropanetetraacetic acid iron ammonium one water salt 113 170

Ammonium bromide 70 105

Ammonium nitrate 14 21

Succinic acid 34 51

Maleic acid 28 42

Add water to 1.0 liters 1.0 liters

PH (regulating) 4.6 4.0 with ammoniacal liquor.

(stop bath (1) jar liquid)

Above-mentioned bleaching tank liquid and the mixed liquor of remembering 5: 95 (volumetric ratio) of fixing tank liquid down

(pH8.6)

(photographic fixing (2)) jar liquid (gram) replenishes liquid (gram)

240 milliliters 720 milliliters of thiosulfuric acid aqueous ammoniums

(750 grams per liter)

Imidazoles 7 21

Methane thiosulfonic acid ammonium 5 15

Methane sulfinic acid ammonium 10 30

Ethylenediamine tetraacetic acid 13 39

Add water to 1.0 liters 1.0 liters

PH (with ammoniacal liquor, acetate adjustment) 7.4 7.45.

(washing water)

Tap water is fed in the mixed bed formula post that is filled with H type storng-acid cation exchange resin (the system ア of ロ one system ア Application De Ha one ス society Application バ one ライト IR-120B) and OH type strong-base anion-exchange resin (with ア Application バ one ライト IR-400), calcium and magnesium ion concentration are dropped to below the 3mg/L, add Dichloroisocyanuric Acid sodium 20mg/L and sodium sulphate 150mg/L then.The pH value of this solution is in the 6.5-7.5 scope.

(stabilizing solution) jar liquid, the general (unit: gram) of additional liquid

SPTS 0.03

Polyoxyethylene is to single nonylplenyl ether 0.2

(average degree of polymerization 10)

1,2-benzisothiazole-3-ketone sodium 0.10

Disodium EDTA 0.05

1,2,4-triazole 1.3

1, two (1,2, the 4-triazol-1-yl methyl) piperazines 0.75 of 4-

Add water to 1.0 liters

pH???????????????????????????????????????8.5。

(estimate 1: sensitivity)

Use above-mentioned sample, the gelatin filter SC-39 by Fuji Photo film Co., Ltd. makes after continuous wedge exposure 1/100, carries out above-mentioned colour development and handles, and obtains sensitometric curve, has estimated the sensitivity (S0.2Y) of cyan concentration photographic fog+0.2.Numerical value is to put down in writing with the relative sensitivity with respect to sample 101.Numerical value is big more, and sensitivity is high more, unreasonablely thinks.

(estimate 2: graininess)

Use above-mentioned sample, the light quantity that adds 0.2 concentration with formation photographic fog concentration is exposed equally, after having implemented above-mentioned development treatment, utilize the method for being put down in writing on 619 pages among " the ザセオリ one オ Block ザ Off オトグラ Off イッ Network プロセス " that マ Network ラミ Application company publishes to measure.

As can be seen from Table 5, silver halide photographic sensitive material of the present invention is a kind of sensitivity height and the good sensitive photographic material of graininess.

(embodiment 2)

The protective seam thickness of sample 101 is 3.5 μ m.Adjust the gelatin amount in the 15th layer and the 16th layer in the sample 101; make protective layer thickness into 2.5 μ m and 1.5 μ m; and the 6th layer emulsion Em-A-1 is altered to Em-A-4～6 of record in the table 5, and in the 6th layer, add compound of the present invention again, make sample 201～217.Its structure is shown among the table 6.

(estimate 1: sensitivity)

Adopt similarly to Example 1 method to estimate.

(estimate 2: graininess)

Adopt similarly to Example 1 method to estimate.

(estimate 3: sharpness)

Use above-mentioned sample, gelatin filter SC-39 by the manufacturing of Fuji Photo film Co., Ltd., after estimating with pattern, carry out above-mentioned colour development and handle, to represent the sharpness of cyan concentration with respect to the relative value of sample 201 with the white exposure formation MTF under 1/100 exposure.Numerical value is big more, and sharpness is high more, unreasonablely thinks.

Evaluation result is shown among the table 6.The result can access the good silver-halide color of sensitivity height and graininess and distinctiveness million photosensitive materials by combination of the present invention as can be seen thus.

Table 6

Sample	The emulsion name	Use layer	A satisfies condition ^*Particle shared ratio (%) in all particles	Compound (0.156g/m of the present invention ²)	Protective layer thickness summation (μ m)	Relative sensitivity	Graininess	Relative articulation	Remarks
Sample	The emulsion name	Use layer		Compound (0.156g/m of the present invention ²)	Protective layer thickness summation (μ m)	Relative sensitivity	Graininess	Relative articulation	Remarks	??201	??Em-A-1	High sensitivity sense red beds	????25	Do not have	????3.5	??100	????100	??100	Comparative example
??202	??Em-A-1	High sensitivity sense red beds	????25	????HET3	????3.5	??105	????100	??100	Comparative example	??201	??Em-A-1	High sensitivity sense red beds	????25	Do not have	????3.5	??100	????100	??100	Comparative example
??202	??Em-A-1	High sensitivity sense red beds	????25	????HET3	????3.5	??105	????100	??100	Comparative example	??203	??Em-A-1	High sensitivity sense red beds	????25	Do not have	????2.5	??101	????100	??107	Comparative example
??204	??Em-A-1	High sensitivity sense red beds	????25	????HET3	????2.5	??105	????100	??105	Comparative example	??203	??Em-A-1	High sensitivity sense red beds	????25	Do not have	????2.5	??101	????100	??107	Comparative example
??204	??Em-A-1	High sensitivity sense red beds	????25	????HET3	????2.5	??105	????100	??105	Comparative example	??205	??Em-A-4	High sensitivity sense red beds	????80	Do not have	????3.5	??110	????99	??92	Comparative example
??206	??Em-A-4	High sensitivity sense red beds	????80	????HET3	????3.5	??130	????99	??93	The present invention	??205	??Em-A-4	High sensitivity sense red beds	????80	Do not have	????3.5	??110	????99	??92	Comparative example
??206	??Em-A-4	High sensitivity sense red beds	????80	????HET3	????3.5	??130	????99	??93	The present invention	??207	??Em-A-4	High sensitivity sense red beds	????80	Do not have	????2.5	??118	????99	??109	The present invention
??208	??Em-A-4	High sensitivity sense red beds	????80	????HET3	????1.5	??150	????99	??120	The present invention	??207	??Em-A-4	High sensitivity sense red beds	????80	Do not have	????2.5	??118	????99	??109	The present invention
??208	??Em-A-4	High sensitivity sense red beds	????80	????HET3	????1.5	??150	????99	??120	The present invention	??209	??Em-A-4	High sensitivity sense red beds	????80	????(2)	????1.5	??168	????99	??121	The present invention
??210	??Em-A-4	High sensitivity sense red beds	????80	????(59)	????1.5	??177	????99	??118	The present invention	??209	??Em-A-4	High sensitivity sense red beds	????80	????(2)	????1.5	??168	????99	??121	The present invention
??210	??Em-A-4	High sensitivity sense red beds	????80	????(59)	????1.5	??177	????99	??118	The present invention	??211	??Em-A-4	High sensitivity sense red beds	????80	????(60)	????1.5	??163	????99	??119	The present invention
??212	??Em-A-5	High sensitivity sense red beds	????50	Do not have	????3.5	??100	????100	??100	Comparative example	??211	??Em-A-4	High sensitivity sense red beds	????80	????(60)	????1.5	??163	????99	??119	The present invention
??212	??Em-A-5	High sensitivity sense red beds	????50	Do not have	????3.5	??100	????100	??100	Comparative example	??213	??Em-A-5	High sensitivity sense red beds	????50	????HET3	????3.5	??115	????100	??101	The present invention
??214	??Em-A-5	High sensitivity sense red beds	????50	Do not have	????1.5	??112	????100	??117	The present invention	??213	??Em-A-5	High sensitivity sense red beds	????50	????HET3	????3.5	??115	????100	??101	The present invention
??214	??Em-A-5	High sensitivity sense red beds	????50	Do not have	????1.5	??112	????100	??117	The present invention	??215	??Em-A-5	High sensitivity sense red beds	????50	????HET3	????1.5	??125	????100	??115	The present invention
??216	??Em-A-6	High sensitivity sense red beds	????40	Do not have	????3.5	??97	????100	??101	Comparative example	??215	??Em-A-5	High sensitivity sense red beds	????50	????HET3	????1.5	??125	????100	??115	The present invention
??216	??Em-A-6	High sensitivity sense red beds	????40	Do not have	????3.5	??97	????100	??101	Comparative example	??217	??Em-A-6	High sensitivity sense red beds	????40	????HET3	????1.5	??105	????99	??103	Comparative example

(embodiment 3)

Prepared emulsion of the present invention with average equivalent bulb diameter identical with emulsion Em-B.This emulsion satisfies the full terms of emulsion of the present invention.The emulsion Em-B of the 5th layer (the red property of middle sensitivity sense emulsion layer) of sample 101 is modified to this emulsion; but also in the 5th layer (the red property of middle sensitivity sense emulsion layer), added compound H ET-3 of the present invention; make its amount reach 0.156 the gram/square metre; and then make protective layer thickness into 1.5 μ m, made silver halide colour photographic sensitive material.The silver halide colour photographic sensitive material of making so of the present invention it is found that also have good similarly to Example 2 effect.

(embodiment 4)

Prepared emulsion of the present invention with identical average equivalent bulb diameter with emulsion Em-F.This emulsion satisfies the full terms of emulsion of the present invention.The emulsion Em-F of the 11th layer (the green property of high sensitivity sense emulsion layer) of sample 101 is modified to this emulsion; but also in 11th layer (the green property of high sensitivity sense emulsion layer), added compound H ET-3 of the present invention; make its amount reach 0.156 the gram/square metre; and then make protective layer thickness into 1.5 μ m, made silver halide colour photographic sensitive material.The silver halide colour photographic sensitive material of making so of the present invention it is found that also have good similarly to Example 2 effect.

Claims

1. silver halide colour photographic sensitive material; on support, have respectively in the silver halide photographic sensitive material of one deck sense indigo plant silver halide emulsion layer at least, the green property silver halide emulsion layer of sense, the red property silver halide emulsion layer of sense and protective seam; it is characterized in that; at least contain in this silver-halide color photoelement and have three heteroatomic compounds that are used to increase the photograph sensitivity in a kind of molecule at least; and contained emulsion is in the one deck at least in this silver halide emulsion layer, by

(i) form by iodine silver bromide or chlorine iodine silver bromide,

(iii) and by do not have year wheel construction and thickness be below the 0.1 μ m the core of forming by the iodine silver bromide with have the shell portion of ten above dislocation lines to constitute,

And with (111) face is the dull and stereotyped particle of first type surface, occupies the photonasty silver emulsion more than 50% of all silver halide particle numbers.

2. silver halide colour photographic sensitive material according to claim 1 is characterized in that, the thickness summation of described protective seam is below 3 μ m.

3. silver halide colour photographic sensitive material according to claim 1 and 2 is characterized in that, having three heteroatomic compounds that are used to increase the photograph sensitivity in the described molecule at least is 1,3,4,6-purine compounds.

4. according to each described silver halide colour photographic sensitive material in the claim 1 to 3, it is characterized in that having three heteroatomic compounds that are used to increase the photograph sensitivity in the described molecule at least, be by remember down general formula (A) or (B) expression compound,

[changing 1]

General formula (A)

In the general formula (A), R ₁Expression hydrogen atom or substituting group, Z represents to form the required non-metallic atom group of five Yuans azoles that contains 2～4 nitrogen-atoms, and this azole also can have substituting group (comprising condensed ring), and X represents hydrogen atom or substituting group;

[changing 2]

General formula (B)

In the general formula (B), Za represents-NH-or-CH (R ₃The respectively independent expression-C (R of)-, Zb and Zc ₄)=or-N=, R ₁, R ₂And R ₃The special substituent constant σ of independent respectively expression Hamann value is at the electron withdraw group more than 0.2, below 1.0, R ₄Wherein, there are two R in expression hydrogen atom or substituting group in formula ₄The time, two R ₄Can be identical or different, X represents hydrogen atom or substituting group.